JP2018145244A - Novel metallo-supramolecular polymer-containing composition and high-efficiency production method of metallo-supramolecular polymer-containing composition using microwaves - Google Patents

Abstract

The present invention provides a novel method for producing a metallo-supramolecular polymer-containing composition, and a novel metallo-supramolecular polymer-containing composition. According to one embodiment of the present invention, at least one kind of organic ligand having a plurality of metal coordination sites and at least one kind of ion of a transition metal and / or a lanthanoid-based metal are subjected to microwave irradiation. A method for producing a metallo supramolecular polymer-containing composition having enhanced structural regularity, comprising forming a metallo supramolecular polymer in which a reaction is caused by internal heating to form a metallo supramolecular polymer in which both are alternately coordinated and bonded. The at least one organic ligand may include an organic ligand having two or more of any of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and a derivative thereof. [Selection diagram] None

Description

The present invention relates to a novel metallo supramolecular polymer (including so-called oligomer) -containing composition and a method for producing a metallo supramolecular polymer-containing composition with high efficiency using microwaves.
Furthermore, this invention relates to the electrochromic element containing a metallo supramolecular polymer containing composition.

  A metallo-supramolecular polymer is a polymer in which metal ions and organic ligands are alternately linked by coordination bonds. Metallo supramolecular polymers exhibit excellent electrochromic properties (electrochemically color changing properties) in response to electrochemical redox of metals. Since it has such electrochromic properties, the metallo supramolecular polymer is expected to be applied to various energy-saving devices such as smart windows (for example, see Patent Document 1). That is, as a material having excellent electrochromic properties, it is desired to develop a metallo supramolecular polymer having both good redox stability, high contrast ratio, high coloring efficiency, switching control function, and high processability.

  However, there has been a limit to the synthesis of metallo supramolecular polymers using conventional synthesis methods. The synthesis of metallo supramolecular polymers that require a high complexation temperature of 150 ° C. or higher, particularly 200 ° C. or higher, is due to the high reaction temperature and long reaction time, and the structure of the ligand as a raw material and the complex of the product. In many cases, the structure is destroyed, and water and oxygen in the reaction system are combined. Accordingly, development of a new method for synthesizing a metallo supramolecular polymer that does not cause such inconvenience is demanded.

  On the other hand, polymer synthesis using microwaves is expected as a next-generation material synthesis method from the viewpoint of greatly shortening the reaction time and reducing wastes such as solvents (for example, see Non-Patent Document 1). For example, techniques for applying microwaves to the production of polylactic acid and polyester have been developed. However, it has not been reported to use this technique for the synthesis of metallo supramolecular polymers, which are generally recognized as difficult to obtain substances having high structural regularity.

Japanese Patent No. 5062712

Practical application of polymer synthesis process using microwave (National Institute of Advanced Industrial Science and Technology), http: // www. aist. go. jp / aist_j / press_release / pr2009 / pr20091104 / pr20091104. html (published on November 4, 2009)

One of the objects of the present invention is to provide a novel method for producing a metallo supramolecular polymer (including so-called oligomer) -containing composition that is not found in the prior art.
Another object of the present invention is to provide a novel metallo-supramolecular polymer-containing composition itself which is not present in the prior art.

The means for solving the above-described problems according to the present invention are as follows.
[1].
A method for producing a metallo-supramolecular polymer-containing composition having improved structural regularity,
At least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are reacted by internal heating by microwave irradiation, and both are alternately Forming a coordinated metallo-supramolecular polymer.
[2].
The above [1], wherein the at least one organic ligand includes an organic ligand having two or more of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and a derivative thereof. The manufacturing method of the metallo supramolecular polymer containing composition of claim | item.
[3].
At least one of the transition metal and / or lanthanoid metal is a metal selected from iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osnium, iridium, platinum, gold, europium, and terbium. A method for producing a metallo-supramolecular polymer-containing composition as described in [1] or [2] above.
[4].
The molar ratio of at least one organic ligand to be subjected to an internal heating reaction by microwave irradiation to at least one ion of a transition metal and / or a lanthanoid metal is 1: 1 to 2: 1. The manufacturing method of the metallo supramolecular polymer containing composition of any one of said [1]-[3] items.
[5].
The metallo supramolecule according to any one of [1] to [4] above, wherein the at least one organic ligand includes an organic ligand having a structure represented by at least one of the following formulas: Method for producing polymer-containing composition:





Here, R is a spacer containing a carbon atom and a hydrogen atom, or a spacer that directly connects any one of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, and an acetylacetonate group, and R ¹ , R ² , R ³ and R ⁴ are all the same, different or partly the same hydrogen atom, aryl group or alkyl group.
[6].
The method for producing a metallo-supramolecular polymer-containing composition according to any one of the above [1] to [5], wherein the internal heating reaction by microwave irradiation is performed at a temperature of 150 ° C. or higher.
[7].
The method for producing a metallo-supramolecular polymer-containing composition according to any one of the above [1] to [6], wherein the metallo-supramolecular polymer-containing composition contains any of oligomers represented by the following structural formulas: .

[8].
A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
For this composition, the absorption signal A due to each proton of the organic ligand at the polymer end in ¹ H-NMR measured under the conditions of solvent CD ₃ OD, predetermined concentration, frequency 300 MHz, and room temperature is the same organic. A metallo-supramolecular polymer-containing composition for reference obtained by performing a reaction until the consumption of raw materials reaches a steady state by external heating at a predetermined temperature required for complex formation, using the same metal ion as the ligand Absorption signal A corresponding to absorption signal A due to each proton of the organic terminal organic ligand in ¹ H-NMR measured under the conditions of solvent CD ₃ OD, same predetermined concentration, frequency 300 MHz, room temperature The above metallo-supramolecular polymer with enhanced structural regularity indicated by a state of less broadening compared to ' Containing composition.
[9].
A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
Electrochromic properties of this composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm Contrast ΔT (%) and / or coloring efficiency η (cm ² / C) uses the same organic ligand and the same metal ion, and the consumption of raw materials is increased by external heating at a predetermined temperature required for complex formation. For the reference metallo-supramolecular polymer-containing composition obtained by carrying out the reaction until reaching a steady state, applied voltage +1.8 V and 0 V, at intervals of 5 seconds, electrolyte solution 0.1 M LiClO ₄ / ACN, ITO electrode Electrochromic contrast ΔT ′ (%) and / or coloring efficiency η ′ (c) measured in the upper working area 1.5 cm × 1.5 cm ^{2 /} C) with enhanced structural regularity represented by the state that larger than that, the metallo supramolecular polymer-containing composition.
[10].
A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
Electrochromic properties of this composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm The metallo-supramolecular polymer-containing composition having a contrast ΔT (%) of 70% or more and / or a coloring efficiency η (cm ² / C) of 320 cm ² / C or more.
[11].
Electrochromic properties of the above composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm The metallo-supramolecular polymer-containing composition according to [9], wherein the contrast ΔT (%) is 70% or more and / or the coloring efficiency η (cm ² / C) is 320 cm ² / C or more.
[12].
[8] The above [8], wherein the at least one organic ligand includes an organic ligand having two or more of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and derivatives thereof. The metallo supramolecular polymer-containing composition according to any one of items [11] to [11].
[13].
At least one of the transition metal and / or lanthanoid metal includes a metal selected from iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osnium, iridium, platinum, gold, europium and terbium. The metallo supramolecular polymer-containing composition according to any one of items [8] to [12] above.
[14].
The above-mentioned items [8] to [13], wherein the molar ratio of the at least one organic ligand to the at least one ion of the transition metal and / or lanthanoid metal is 1: 1 to 2: 1. The metallo supramolecular polymer-containing composition according to any one of the above.
[15].
The metallo supramolecular polymer-containing composition according to any one of the above [8] to [14], comprising a metallo supramolecular polymer having a structure represented by at least one of the following formulas and a counter anion:





Here, R is a spacer containing a carbon atom and a hydrogen atom, or a spacer that directly connects any one of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, and an acetylacetonate group, and R ¹ , R ² , R ³ , R ⁴ are all the same, all different, or partly the same hydrogen atom, aryl group or alkyl group, and M is one or more of transition metal and / or lanthanoid metal N is an integer of 2 or more indicating the degree of polymerization, and counter anions are halide ions such as chloride ions, hydroxide ions, acetate ions, perchlorate ions, carbonate ions, four ions. Boron fluoride ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, (CF ₃ SO ₂ ) ₂ N ion , Polyoxymetalates, or combinations thereof.
[16].
The metallo-supramolecular polymer-containing composition according to any one of the above-mentioned [8] to [15], comprising any oligomer represented by the following structural formula.

[17].
The first transparent electrode, the second transparent electrode, and any one of the above-mentioned [8] to [16], which is located between the first transparent electrode and the second transparent electrode. An electrochromic device comprising a metallo supramolecular polymer-containing composition.

According to the production method of the present invention, by using microwave irradiation under appropriate conditions, a metallo supramolecular polymer (so-called oligomer) having a small chemical structure defect of a raw material ligand, that is, having a high structure regularity. Containing composition) can be efficiently obtained in a short time (while suppressing waste of energy).
Further, such a metallo-supramolecular polymer-containing composition having a high structural regularity has improved electrochromic properties and can be suitably used as a raw material for an electrochromic device.

The transition of the power (W) and temperature (° C.) of the reactor in Synthesis Example 1 (polymer synthesis) is shown. (A) The transition of the power (W) and temperature (° C.) of the reactor in Synthesis Example 2 (10-mer oligomer synthesis) is shown. (B) Changes in the power (W) and temperature (° C.) of the reactor in Synthesis Example 3 (pentamer oligomer synthesis) are shown. (C) Changes in power (W) and temperature (° C.) of the reactor in Synthesis Example 4 (monomer oligomer synthesis) are shown. The result of having measured the UV-Vis spectrum about the polymer obtained by the synthesis example 1 and the polymer obtained by the comparative synthesis example on condition of solvent methanol and a density | concentration of 25 micromol is shown. (A) About the polymer obtained by the synthesis example 1, and the polymer obtained by the comparative synthesis example, the result of having measured the photoluminescence spectrum on the conditions of solvent methanol, density | concentration 25 micromol, (lambda) _ex = 310nm is shown. (B) About the polymer obtained by the synthesis example 1, and the polymer obtained by the comparative synthesis example, the result of having measured the photoluminescence spectrum on the conditions of solvent methanol, density | concentration 25 micromol, (lambda) _ex = 515nm is shown. The result of having measured the UV-Vis spectrum on the polymer obtained by the synthesis example 1 and the polymer obtained by the comparative synthesis example on condition of solvent DMSO and a density | concentration of 25 micromol is shown. (A) About the polymer obtained by the synthesis example 1, and the polymer obtained by the comparative synthesis example, the result of having measured the photoluminescence spectrum on the conditions of solvent DMSO, density | concentration 25 micromol, (lambda) _ex = 310nm is shown. (B) For the polymer obtained in Synthesis Example 1, the 10-mer oligomer obtained in Synthesis Examples 2 to 4, the pentamer oligomer, the monomer oligomer, and the polymer obtained in Comparative Synthesis Example, the solvent DMSO, The result of having measured the photoluminescence spectrum on conditions with a density | concentration of 25 micromol and (lambda) _ex = 510nm is shown. The result obtained by measuring ¹ H-NMR of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example under the conditions of solvent CD ₃ OD, frequency of 300 MHz, and room temperature is shown. The result of having performed TGA (thermogravimetric analysis) about the polymer obtained by the synthesis example 1 and the polymer obtained by the comparative synthesis example on condition of 10 degree-C / min of scanning speeds under nitrogen is shown. (A) About the polymer obtained by the comparative synthesis example, the external appearance photograph at the time of visually observing the coloring change of the ITO electrode when the voltage of 0.0V and + 1.8V is applied is shown. (B) The as-cast state and the light transmittance (%) of each polymer when 0.0 V and +1.8 V are applied are shown on the vertical axis and the wavelength (nm) is shown on the horizontal axis. . (C) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of the same polymer when a voltage is repeatedly applied while the insertion interval is changed to 10 seconds, 5 seconds or 2 seconds. (A) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of the polymer obtained in the comparative synthesis example up to 0 to 100 seconds when the voltage application interval is 10 seconds is shown. (B) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of this polymer from 20 to 40 seconds when the voltage application interval is 10 seconds. (A) About the polymer obtained by the synthesis example 1, the external appearance photograph at the time of visually observing the coloring change of the ITO electrode when the voltage of 0.0V and + 1.8V is applied is shown. (B) The as-cast state, and when 0.0V and + 1.8V are applied, the light transmittance (%) of the same polymer is plotted on the vertical axis, and the wavelength (nm) is plotted on the horizontal axis. Show. (C) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of the same polymer when a voltage is repeatedly applied while the insertion interval is changed to 10 seconds, 5 seconds or 2 seconds. (A) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of the polymer obtained in Synthesis Example 1 up to 0 to 100 seconds when the voltage application interval is 10 seconds is shown. (B) The time-dependent change (electrochemical responsiveness) of the light transmittance (%) of this polymer from 20 to 40 seconds when the voltage application interval is 10 seconds. (C) Permeability loss (%) with respect to current (A) for each sample of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example is shown. The result of having measured the UV-Vis spectrum on the conditions of solvent methanol and a density | concentration of 25 micromol about the polymer obtained by the synthesis example 1, the oligomer obtained by the synthesis examples 2-4, and the polymer obtained by the comparative synthesis example is shown. The result of having measured the UV-Vis spectrum on the conditions of solvent DMSO and a density | concentration of 25 micromol about the polymer obtained by the synthesis example 1, the oligomer obtained by the synthesis examples 2-4, and the polymer obtained by the comparative synthesis example is shown. (A) Photoluminescence of the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example under the conditions of solvent methanol, concentration 25 μM, λ _ex = 310 nm. The result of having measured the spectrum is shown. (B) For the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, photoluminescence was performed under the conditions of solvent methanol, concentration 25 μM, λ _ex = 515 nm. The result of having measured the spectrum is shown. (A) For the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, photoluminescence was performed under the conditions of solvent DMSO, concentration 25 μM, λ _ex = 310 nm. The result of having measured the spectrum is shown. (B) For the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, photoluminescence was performed under the conditions of solvent DMSO, concentration 25 μM, λ _ex = 510 nm. The result of having measured the spectrum is shown. For the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, TGA (thermogravimetric analysis) was performed at a scanning speed of 10 ° C./min and under conditions of nitrogen. The results are shown. The results of X-ray diffraction performed on the polymer obtained in Synthesis Example 1 and the oligomers obtained in Synthesis Examples 2 to 4 under the conditions of a scanning speed of 0.02 / step and CuKα are shown. About the monomer oligomer obtained in the synthesis example 4, the reference sign of each hydrogen regarding NMR measurement is shown. For monomeric oligomer obtained in Synthesis Example 4, it shows the solvent _CD 3 OD, frequency 300MHz, the results of measurement of ^{1 H-NMR (COSY-NMR} ) under the conditions of room temperature. About the pentamer oligomer obtained in Synthesis Example 3, reference numerals of each hydrogen relating to NMR measurement, and the results of ¹ H-NMR measurement of this oligomer under the conditions of solvent CD ₃ OD, frequency 300 MHz, and room temperature . About the 10-mer oligomer obtained in Synthesis Example 2, the reference sign of each hydrogen relating to NMR measurement, and the results of ¹ H-NMR measurement of this oligomer under the conditions of solvent CD ₃ OD, frequency 300 MHz, room temperature . The COSY-NMR measurement result about the 10-mer oligomer obtained in Synthesis Example 2 is shown together with the reference numerals of the respective hydrogens. The NMR measurement results for the 10-mer oligomer, pentamer oligomer, and monomer oligomer obtained in Synthesis Examples 2 to 4 are also shown. The polymer obtained in Synthesis Example 1, the reference numeral of each of the hydrogen regarding NMR measurement, and for this polymer shows solvent _CD 3 OD, frequency 300MHz, the result was analyzed by ¹ H-NMR under the condition at room temperature.

In the method for producing a metallo-supramolecular polymer-containing composition according to the present invention, at least one organic ligand having a plurality of metal coordination sites used as a raw material is particularly limited as long as it has a plurality of metal coordination sites. It is not a thing. Typically, an organic ligand having any two or more of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and derivatives thereof can be given.
These organic ligands may have a substituent. When it has a substituent, the structure of the substituent is not particularly limited. For example, it is a branched or straight chain alkyl group having 1 to 20 carbon atoms, and may have 6 to 20 carbon atoms which may contain a hetero atom. Of the aryl group.

In the method for producing a metallo-supramolecular polymer-containing composition according to the present invention, at least one ion of a transition metal and / or lanthanoid metal used as a raw material is not particularly limited as long as it is a metal ion belonging to these groups. is not. Typically, a metal selected from iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osnium, iridium, platinum, gold, europium, and terbium. In addition, at least one ion of a transition metal and / or a lanthanoid metal can be used in the form of a salt formed with a counter anion. Examples of counter anions include, but are not limited to, halide ions such as chloride ions, hydroxide ions, acetate ions, perchlorate ions, carbonate ions, boron tetrafluoride ions, hexafluorophosphate ions, trifluoro ions. Examples include romethanesulfonic acid ions, (CF ₃ SO ₂ ) ₂ N ions, polyoxymetalates, or combinations thereof.

  The molar ratio of at least one organic ligand and at least one ion of a transition metal and / or lanthanoid metal used for an internal heating reaction by microwave irradiation is not particularly limited, but is usually 1: It is 1-2: 1. More typically, this molar ratio is from 1: 1 to 1.5: 1.

According to a general definition, the microwave is an electromagnetic wave having a frequency of 300 MHz to 3 THz. The magnetron frequency of microwave irradiation that can be typically used is not particularly limited, but is about 300 MHz to 30 GHz, and preferably about 900 to 6,000 MHz from the viewpoint of availability. .
Microwaves are usually irradiated continuously, but because the reaction system quickly rises to a predetermined temperature due to irradiation, it is possible to irradiate intermittently without always irradiating microwaves. . Moreover, after reaching the optimum polymerization reaction temperature, the microwave output may be controlled so that a constant temperature can be maintained.
The production method according to the present invention can usually be carried out using only internal heating by microwave irradiation (without using external heating). In addition to internal heating by microwave irradiation, a general heating method by external heating can be used in combination.

The reaction temperature of the internal heating reaction by microwave irradiation depends on the complex structure of the target metallo-supramolecular polymer and is not particularly limited, but is usually performed at a temperature of 100 ° C. or higher. This reaction temperature may be 150 ° C. or higher, 180 ° C. or higher, and 200 ° C. or higher.
When the reaction temperature required to obtain the complex structure of the desired metallo-supramolecular polymer is such a high temperature, according to the conventional external heating method, the structure and formation of the ligand that is the raw material during a long reaction time In many cases, the complex structure of the product is destroyed, and there are disadvantages such as bonding of water and oxygen in the reaction system. According to the present invention, such an internal heating reaction by microwave irradiation is adopted. Inconvenience is solved, and a polymer having a high degree of structural regularity can be obtained efficiently (energy saving) in a short time. Therefore, the higher the temperature required for complex formation, the greater the advantage of the present invention.

  The reaction time of the internal heating reaction by microwave irradiation (theoretically, the time required to complete the reaction when the raw material consumption reaches a steady state) is not particularly limited, but may be, for example, 3 hours or less. The reaction time is preferably 1 hour or less, more preferably 30 minutes or less, and most preferably 10 minutes or less. Although it does not specifically limit as a minimum of reaction time, For example, it is 30 second or more, 1 minute or more, or 2 minutes or more.

  The internal heating reaction by microwave irradiation can be performed under reflux by dispersing the above raw materials in a suitable organic solvent. An organic solvent having a boiling point higher than the required reaction temperature is appropriately selected, but is not particularly limited. Examples of the solvent include ethylene glycol. After the reaction, the solid is usually obtained by distilling off the organic solvent and concentrating, followed by reprecipitation.

The at least one organic ligand having a plurality of metal coordination sites used as a raw material for the production method is, for example, at least one bisterpyridine derivative represented by the following formula (1-1), At least one bipyridine derivative represented by the formula (1-2), at least one pyridine derivative represented by the following formula (1-3), and at least 1 represented by the following formula (1-4) It may be a kind of phenanthroline derivative, at least one acetylacetone derivative represented by the following formula (1-5), or a combination of these.





Here, R is a spacer containing a carbon atom and a hydrogen atom, or a spacer that directly connects any one of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, and an acetylacetonate group, and R ¹ , R ² , R ³ and R ⁴ are all the same, different or partly the same hydrogen atom, aryl group or alkyl group.

  As an alternative embodiment of the bisterpyridine derivative, a compound having a structure in which a methylene group is bridged between (at least one of) two adjacent pyridine rings can also be used.

The spacers in the formulas (1-1) to (1-5) are branched or straight chain alkylene groups having 1 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms that may contain a hetero atom. It's okay. The spacer may be an arylene group represented by any of the following formulas (2) to (5), for example.

When R ¹ , R ² , R ^3, and R ⁴ are an aryl group or an alkyl group other than a hydrogen atom, a branched or straight chain alkyl group having 1 to 20 carbon atoms and a carbon atom that may contain a hetero atom 6 May be ˜20 aryl groups. The alkyl group or aryl group may be, for example, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, a phenyl group, or a toluyl group, but is not limited thereto. Moreover, these aryl groups or alkyl groups may further have a substituent. Examples of such a substituent include an alkyl group such as a methyl group, an ethyl group, and a hexyl group, an alkoxy group such as a methoxy group and a butoxy group, and a halogen group such as chlorine and bromine.

The metallo supramolecular polymer-containing composition according to the present invention can be obtained by the production method according to the present invention described above.
The at least one organic ligand having a plurality of metal coordination sites, at least one ion of a transition metal and / or a lanthanoid metal in the metallo-supramolecular polymer-containing composition according to the present invention is not particularly limited, The production method according to the present invention may be as described above.

An example of a metallo supramolecular polymer (a polymer having a structure for production) contained in this composition is when the organic ligand is a bisterpyridine derivative, a bipyridine derivative, a pyridine derivative, a phenanthroline derivative, or an acetylacetone derivative Can be represented by the following general formulas (6-1) to (6-5). The meanings of the symbols R, R ¹ , R ² , R ³ and R ^{4 in} the formula are the same as those described for the bisterpyridine derivative represented by the formula (1-1), and M is a transition metal and One or more kinds of metal ions which are / or lanthanoid metals, and n is an integer of 2 or more indicating the degree of polymerization. In the structures of the general formulas (6-1) to (6-5), a counter anion (not shown in the formula) corresponding to the valence of the metal ion M is ionically bonded. The counter anion is not particularly limited, but halide ions such as chloride ions, hydroxide ions, acetate ions, perchlorate ions, carbonate ions, boron tetrafluoride ions, hexafluorophosphate ions, trifluoromethanesulfonic acid. It may be an ion, (CF ₃ SO ₂ ) ₂ N ion, polyoxymetallate, or a combination thereof.

  The above specific examples of metallo-supramolecular polymers are disubstituted, but not limited to this, depending on the type and valence of the metal ion used, 3 and 4 or more coordination structures can also be produced. Can do.

In this specification, the term “metallo-supramolecular polymer” refers to a so-called oligomer (for example, 10 to 10 from a monomer when a structural portion in which a predetermined number of organic ligands are coordinated to one metal ion is used as one repeating unit. Polymers including polymer etc.) are meant.
For example, 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6 ′, 2 ′ ′-terpyridine) is used as the organic ligand, and RuCl ₂ (dmso) ₄ as the metal complex. The monomer oligomer, pentamer oligomer, and 10mer oligomer obtained by using can be represented by the following general formula (7).

  In the case of polymer production excluding so-called oligomers for the metallo supramolecular polymer-containing composition according to the present invention, the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography is usually about 5000 to 300,000. There is no particular limitation. The weight average molecular weight Mw may be about 10,000 to 200,000.

The metallo-supramolecular polymer-containing composition according to the present invention usually contains a metallo-supramolecular polymer having a target structure (that is, a polymer having a structure in which organic ligands and metal ions are alternately coordinated) in a majority amount. However, it inevitably contains impurities such as metallo supramolecular polymers having an unintended structure generated during production.
In the conventional production method by external heating, when synthesizing a metallo supramolecular polymer that requires a complex formation temperature of 150 ° C. or higher, particularly 200 ° C. or higher, the raw material coordination is caused by the high reaction temperature and long reaction time. In many cases, the structure of the child or the complex structure of the product is destroyed, and water and oxygen in the reaction system are combined. The metallo-supramolecular polymer-containing composition according to the present invention is preferably manufactured using microwave irradiation, thereby destroying the structure of the raw material ligand and the complex structure of the product, and binding of water and oxygen in the reaction system. Is suppressed and has high structural regularity. Such a metallo-supramolecular polymer-containing composition having a high structure regularity has improved electrochromic properties and can be suitably used as a raw material for an electrochromic device.

The degree of improvement in the structure regularity of the metallo-supramolecular polymer-containing composition according to the present invention (in other words, the content of the metallo-supramolecular polymer having a target structure in which organic ligands and metal ions are alternately coordinated is conventionally The degree of improvement compared to the technology) is mainly due to the comparison of the absorption signal due to each proton of the polymer-terminated organic ligand in ¹ H-NMR or the contrast ΔT (%) of the electrochromic properties, It can be objectively grasped by comparing the coloring efficiency η (cm ² / C).

Accordingly, in one embodiment, the metallo-supramolecular polymer-containing composition according to the present invention comprises at least one organic ligand having a plurality of metal coordination sites and at least one of a transition metal and / or a lanthanoid metal. A metallo-supramolecular polymer-containing composition in which ions are alternately coordinate-bonded, and a polymer in ¹ H-NMR measured for this composition under conditions of solvent CD ₃ OD, predetermined concentration, frequency of 300 MHz, and room temperature Absorption signal A attributed to each proton of the terminal organic ligand uses the same organic ligand and the same metal ion, and the raw material consumption is in a steady state by external heating at a predetermined temperature required for complex formation. for reference metallo supramolecular polymer containing composition obtained by carrying out the reaction up to the solvent CD 3 _OD, the same predetermined concentration, peripheral The number 300MHz, due to the proton of the organic ligands of the polymer ends in ^{1 H-NMR} measured at conditions of room temperature, broadening compared to absorption signal A 'which corresponds to the absorption signal A is smaller (or signal Sharper, preferably greater in signal (peak) height, or larger in signal (peak) integrated area, preferably greater in signal (peak) integrated area by about 5%, more preferably in signal (peak) With an increased structural regularity indicated by the condition that the integrated area is about 10% greater).
As used herein, “each proton of the organic ligand at the polymer terminal” refers to at least one proton of the organic ligand at the polymer terminal, preferably two or more protons of the organic ligand at the polymer terminal, and more Preferably, it refers to all protons of the organic ligand at the end of the polymer.
Further, in this embodiment, “obtained by carrying out the reaction until the consumption of raw materials reaches a steady state by external heating at a predetermined temperature required for complex formation, using the same organic ligand and the same metal ion. In addition to the factors specified here, the manufacturing conditions of the “metallo-supramolecular polymer-containing composition” include the present invention for some or all of the various factors such as the type of solvent used, reaction temperature, reaction pressure, and reaction time. It is desirable to employ the same conditions as the production conditions of the metallo-supramolecular polymer-containing composition according to the invention (except for the use of microwave internal heating) (the same applies to the following embodiments).
“Predetermined temperature” in the case of “reacting until the raw material consumption reaches a steady state by external heating at the predetermined temperature required for complex formation using the same organic ligand and the same metal ion” Is, in one embodiment, the lowest temperature that can provide activation energy for complex formation or above, and in another embodiment, can be brought to reflux when the complexing reaction is conducted under reflux. The minimum temperature or above. This description applies to the following embodiments as well.

In another embodiment, the metallo-supramolecular polymer-containing composition according to the present invention includes at least one organic ligand having a plurality of metal coordination sites, and at least one transition metal and / or lanthanoid metal. Is a metallo-supramolecular polymer-containing composition alternately coordinated, and applied voltage +1.8 V and 0 V, 5 seconds interval, 0.1 M LiClO ₄ / ACN electrolyte solution, The same organic ligand and the same metal with contrast ΔT (%) and / or coloring efficiency η (cm ² / C) of electrochromic properties measured in a working area of 1.5 cm × 1.5 cm on the ITO electrode And a reference mem- ber obtained by performing a reaction until the raw material consumption reaches a steady state by external heating at a predetermined temperature required for complex formation. For the Taro supramolecular polymer-containing composition, measured at applied voltage +1.8 V and 0 V, 5 sec interval, electrolyte solution 0.1 M LiClO ₄ / ACN, working area on ITO electrode 1.5 cm × 1.5 cm. It is larger than the contrast ΔT ′ (%) and / or coloring efficiency η ′ (cm ² / C) of the electrochromic characteristics (preferably, the contrast ΔT (%) is larger by 5% or more, more preferably the contrast ΔT (%). Is more than 10%, more preferably the contrast ΔT (%) is more than 15% and / or the coloring efficiency η (cm ² / C) is more than 5%, more preferably the coloring efficiency η (cm ² / C) increases more is 10% or more, more preferably Jo that coloring efficiency η ^(cm 2 / C) of more more than 15% greater) With enhanced structural regularity represented by.

In yet another embodiment, the metallo-supramolecular polymer-containing composition according to the present invention comprises at least one organic ligand having a plurality of metal coordination sites, and at least one of a transition metal and / or a lanthanoid metal. Is a metallo-supramolecular polymer-containing composition alternately coordinated, and applied voltage +1.8 V and 0 V, 5 seconds interval, 0.1 M LiClO ₄ / ACN electrolyte solution, The contrast ΔT (%) of the electrochromic properties measured at a working area of 1.5 cm × 1.5 cm on the ITO electrode is 70% or more and / or the coloring efficiency η (cm ² / C) is 320 cm ² / C. That's it. This contrast ΔT (%) is preferably 75% or more, and more preferably 78% or more. The coloring efficiency η (cm ² / C) is preferably 340 cm ² / C or more, and more preferably 360 cm ² / C or more.

In yet another embodiment, the metallo-supramolecular polymer-containing composition according to the present invention comprises at least one organic ligand having a plurality of metal coordination sites, and at least one of a transition metal and / or a lanthanoid metal. Is a metallo-supramolecular polymer-containing composition alternately coordinated, and applied voltage +1.8 V and 0 V, 5 seconds interval, 0.1 M LiClO ₄ / ACN electrolyte solution, The same organic ligand and the same metal with contrast ΔT (%) and / or coloring efficiency η (cm ² / C) of electrochromic properties measured in a working area of 1.5 cm × 1.5 cm on the ITO electrode And a reference mem- ber obtained by performing a reaction until the raw material consumption reaches a steady state by external heating at a predetermined temperature required for complex formation. For the Taro supramolecular polymer-containing composition, measured at applied voltage +1.8 V and 0 V, 5 sec interval, electrolyte solution 0.1 M LiClO ₄ / ACN, working area on ITO electrode 1.5 cm × 1.5 cm. Having an increased structural regularity indicated by the state of being large compared to the contrast ΔT ′ (%) of electrochromic properties and / or the coloring efficiency η ′ (cm ² / C), and for this composition, The contrast ΔT (%) of the electrochromic characteristics measured at applied voltages +1.8 V and 0 V, at intervals of 5 seconds, electrolyte solution 0.1 M LiClO ₄ / ACN, working area on ITO electrode 1.5 cm × 1.5 cm 70% or more (preferably 75% or more, more preferably 78% or more) and / or coloring efficiency η (cm ² / C) is 3 It is 20 cm ² / C or more (preferably 340 cm ² / C or more, more preferably 360 cm ² / C or more).

Other indexes related to the contrast ΔT (%) of electrochromic characteristics and the coloring efficiency η (cm ² / C) include a decoloring rate T _bleached (%), a coloring rate T _colored (%), and a decoloring time t _bleaching ( Second) and coloring time _tcoloring (seconds), and based on these indicators, the degree of improvement in the structural regularity of the metallo-supramolecular polymer-containing composition according to the present invention can be objectively grasped.

The ¹ H-NMR measurement conditions, the electrochromic contrast contrast ΔT (%), and the coloring efficiency η (cm ² / C) measurement conditions for the metallo-supramolecular polymer-containing composition are the same as the predetermined conditions described in the above embodiments. It is not limited. As long as these measurement conditions are objectively specified conditions and can be compared under the same conditions as the product using the external heating method, conditions different from the above can be set as appropriate.

  The metallo-supramolecular polymer-containing composition according to the present invention may contain an appropriate amount of an optional component depending on the purpose. Examples of such optional components include additives such as lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, mold release agents, and surfactants. The amount of such an optional component can usually be 5% by mass or less.

The metallo supramolecular polymer-containing composition according to the present invention can form an electrochromic device by being positioned between the first transparent electrode and the second transparent electrode. Any known transparent electrode can be used, and examples thereof include a SnO ₂ film, an In ₂ O ₃ film, and an ITO film that is a mixture thereof. The first transparent electrode and the second transparent electrode can be formed on a transparent substrate such as a glass substrate by any physical or chemical vapor deposition method. Application | coating on the 1st transparent electrode of a metallo supramolecular polymer containing composition can be performed by spin coating, dip coating, etc., for example. The electrochromic device may further include a polymer solid electrolyte between the first transparent electrode and the metallo-supramolecular polymer-containing composition. The polymer solid electrolyte is formed by dissolving an electrolyte in a matrix polymer and may have a colorant to improve contrast. During operation of the electrochromic device, the first transparent electrode and the second transparent electrode are connected to a power source, and a predetermined voltage is applied to the metallo supramolecular polymer-containing composition and the polymer solid electrolyte. Thereby, the oxidation-reduction (coloring and decoloring) of the metallo supramolecular polymer-containing composition can be controlled.

  The metallo-supramolecular polymer-containing composition according to the present invention objectively grasps the degree of improvement in structural regularity, thereby defining the extension of the invention, but as long as it is obtained by an organic synthesis reaction, As described above, normally, in addition to the metallo-supramolecular polymer having the target structure, impurities such as a metallo-supermolecular polymer having a structure other than the target generated during the production are inevitably included. It is extremely difficult technically, economically, and laborably to identify and analyze all the components contained in this composition and to define the invention relating to the composition by the structure and ratio of all the components. is there. From such a point of view, the metallo-supramolecular polymer-containing composition according to the present invention can be expressed as an embodiment that refers to the composition itself produced by the above specific production method.

Synthesis Example 1: Synthesis of Ru-based metallo supramolecular polymer by microwave irradiation Organic ligand 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6 ′, 2 ′ ′-terpyridine ) 50.0 mg (0.0925 mmol) and metal complex RuCl ₂ (dmso) ₄ 44.8 mg (0.0925 mmol) in 50 ml ethylene glycol at a set temperature of 197 ° C. under microwave irradiation at 2.45 GHz , Reacted for 60 minutes. Microwave irradiation was performed using SMW-087 (μReactor (registered trademark), manufactured by Shikoku Keiki Kogyo Co., Ltd.). The reaction temperature was measured using a fluorescent fiber thermometer AMOTH FL-2000 (manufactured by Anritsu Keiki Co., Ltd.).
The above mixture and ethylene glycol were put into a heat-resistant glass container having a condenser connected to the top, and the reaction product was irradiated with microwaves while stirring with a magnetic stirrer. The power was automatically controlled according to the set temperature. The reaction was carried out while refluxing the solvent. After completion of the reaction, the solvent was distilled off until the volume reached about 10 ml, followed by concentration, and then the concentrate was added to 200 ml of THF with stirring for reprecipitation. The precipitate was collected by filtration. The yield was 72.4 mg. The transition of the power (W) and temperature (° C.) of the reactor in this synthesis is shown in FIG.

Synthesis Example 2: Synthesis of Ru-based metallo supramolecular decameric oligomer by microwave irradiation Organic ligand 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6 ′, 2 '' -Terpyridine) 50.0 mg (0.0925 mmol) and metal complex RuCl ₂ (dmso) ₄ 40.7 mg (0.0841 mmol) were mixed in 50 ml of ethylene glycol at a set temperature of 197 ° C. at 2.45 GHz. The reaction was carried out for 60 minutes under microwave irradiation to obtain a 10-mer oligomer of Ru metallo supramolecule. The synthesis procedure and the measurement of microwave irradiation and reaction temperature were the same as in Synthesis Example 1. Reprecipitation was performed in the same manner as in Synthesis Example 1 to isolate the product. The yield was 75.1 mg. The transition of the power (W) and temperature (° C.) of the reactor in this synthesis is shown in FIG.

Synthesis Example 3: Synthesis of pentamer oligomer of Ru metallo supramolecule by microwave irradiation Organic ligand 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6 ′, 2 '' -Terpyridine) 50.0 mg (0.0925 mmol) and metal complex RuCl ₂ (dmso) ₄ 37.3 mg (0.0770 mmol) were mixed in 50 ml of ethylene glycol at a set temperature of 197 ° C. at 2.45 GHz. The reaction was carried out for 60 minutes under microwave irradiation to obtain a pentamer oligomer of Ru metallo supramolecule. The synthesis procedure and the measurement of microwave irradiation and reaction temperature were the same as in Synthesis Example 1. Reprecipitation was performed in the same manner as in Synthesis Example 1 to isolate the product. The isolated yield was 27.0 mg. The solvent of the treated filtrate was distilled off, dried and recrystallized with THF to obtain an additional 40.2 mg of solid. The transition of the power (W) and temperature (° C.) of the reactor in this synthesis is shown in FIG.

Synthesis Example 4: Synthesis of monomer oligomer of Ru metallo supramolecule by microwave irradiation Organic ligand 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6 ′, 2 '' -Terpyridine) 50.0 mg (0.0925 mmol) and metal complex RuCl ₂ (dmso) ₄ 22.4 mg (0.0462 mmol) were mixed in 50 ml of ethylene glycol at a set temperature of 197 ° C. at 2.45 GHz. A monomer oligomer of Ru-based metallo supramolecule reacted for 60 minutes under microwave irradiation was obtained. The synthesis procedure and the measurement of microwave irradiation and reaction temperature were the same as in Synthesis Example 1. The solvent of the reaction product was distilled off, dried, and recrystallized with THF to obtain 52.3 mg of a solid. The transition of the power (W) and temperature (° C.) of the reactor in this synthesis is shown in FIG.

Comparative Synthesis Example: Synthesis of Ru-based metallo supramolecular polymer by external heating An organic ligand 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis (2,2 ′: 6) was added to a 10 L four-necked flask. ', 2''-terpyridine) 6.80g (12.6mmol) and ethylene glycol 6.8L were added, and it stirred with the stirring blade at room temperature with the mechanical stirrer. Next, 46.09 g (12.6 mmol) of a metal complex RuCl ₂ (dmso) was added, heated with a mantle heater, and reacted under reflux conditions for 24 hours. The reaction solution was allowed to cool to room temperature, then poured into 10 volumes of THF and allowed to stand overnight to precipitate a solid. The solid was recovered from this solution by centrifugation (9000 rpm × 10 min). The collected solid was put into THF, suspended and washed, and then filtered under reduced pressure using a PTFE filter having a pore size of 1.0 μm. The filtrate was collected and dried in a vacuum dryer at 80 ° C. for 12 hours to obtain a black solid with a total yield of 7.50 g (yield 93%).

FIG. 3 shows the results of measuring the UV-Vis spectrum of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example under the conditions of solvent methanol and a concentration of 25 μM. The polymer obtained in Synthesis Example 1 showed a sharp absorption peak with a large absorbance in charge transfer absorption near 510 nm. In FIG. 3, “Ru-MEPE-mw” means “Ru polymer obtained by microwave irradiation”, and “Ru-MEPE-NARD” means “Ru polymer obtained by external heating” ( This also applies to the subsequent drawings).
The polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example were subjected to photoluminescence under the conditions of solvent methanol, concentration 25 μM, λ _ex = 310 nm, and solvent methanol, concentration 25 μM, λ _ex = 515 nm. The results of measuring the sense spectrum are shown in FIGS. 4 (a) and 4 (b). Under the latter conditions, the emission intensity of the polymer obtained in Synthesis Example 1 was significantly higher than the emission intensity of the polymer obtained in Comparative Synthesis Example.
FIG. 5 shows the results of measuring the UV-Vis spectrum of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example under the conditions of solvent DMSO and concentration of 25 μM. The polymer obtained in Synthesis Example 1 showed a sharp absorption peak with a large absorbance in charge transfer absorption near 520 nm.
Regarding the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example, the conditions were as follows: solvent DMSO, concentration 25 μM, λ _ex = 310 nm; and the polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 4 For the obtained 10-mer oligomer, 5-mer oligomer, monomer oligomer, and polymer obtained in Comparative Synthesis Example, photoluminescence spectrum was measured under the conditions of solvent DMSO, concentration 25 μM, λ _ex = 510 nm. The results are shown in FIGS. 6 (a) and (b). Under the latter conditions, the emission intensity of the 10-mer oligomer, pentamer oligomer, and monomer oligomer obtained in Synthesis Examples 2 to 4 was significantly higher than the emission intensity of the polymer obtained in Comparative Synthesis Example. . In FIG. 6B, “Ru-DP-1” means “Ru oligomer monomer obtained by microwave irradiation”, and “Ru-DP-5” was obtained by microwave irradiation. "Ru oligomer pentamer" means "Ru-DP-10" means "Ru oligomer decamer obtained by microwave irradiation" (the same meaning is used in the following drawings).
FIG. 7 shows the results of ¹ H-NMR measurement of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example under the conditions of solvent CD ₃ OD, frequency 300 MHz, and room temperature. While the polymer obtained in Synthesis Example 1 showed a sharper signal (has higher structural regularity), the signal of the polymer obtained in Comparative Synthesis Example was larger in broadening due to impurities. showed that.
FIG. 8 shows the result of TGA (thermogravimetric analysis) performed on the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example under conditions of a scanning speed of 10 ° C./min and under nitrogen. The polymer obtained in Synthesis Example 1 is considered to have a higher weight loss (%) because it has higher structural regularity and fewer impurities than the polymer obtained in Comparative Synthesis Example.

The cyclic voltammogram measuring apparatus CV50W (manufactured by BAS, Japan) was used to examine the electrochemical response of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example. A working electrode for measurement was prepared by dropping 20 μl of a methanol solution in which each polymer (1 mg, 0.5 ml) was dissolved into each of a GCE (glassy carbon) electrode and an ITO electrode and drying the solution. A Pt counter electrode was used as a counter electrode, and Ag / Ag ⁺ / ACN / TBAP was used as a reference electrode. In either case, the electrodes were made of BAS. The voltage was applied in the range of 0.0 V to +1.8 V, and the voltage insertion interval was 10 seconds, 5 seconds or 2 seconds.

Regarding the polymer obtained in the comparative synthesis example, the color change of the ITO electrode was visually observed when voltages of 0.0 V and +1.8 V were applied (see FIG. 9A). A light orange color was observed when 0.0 V was applied, and a light green color was observed when +1.8 V was applied.
In FIG. 9 (b), the light transmittance (%) of the polymer in the cast state and when 0.0V and + 1.8V are applied are plotted on the vertical axis, and the wavelength (nm) is plotted on the vertical axis. Shown as horizontal axis. FIG. 9 (c) shows the change over time in the light transmittance (%) of the polymer when the insertion interval is changed to 10 seconds, 5 seconds or 2 seconds and a voltage is repeatedly applied (electrochemical response). Indicates. It has been found that the electrochemical response of this polymer decreases when the voltage application interval is changed from 10 seconds to 5 seconds.
FIG. 10 (a) shows the change with time (electrochemical response) of the light transmittance (%) of this polymer from 0 to 100 seconds when the voltage application interval is 10 seconds. Similarly, FIG. 10 (b) shows the time-dependent change (electrochemical response) of the light transmittance (%) of this polymer up to 20 to 40 seconds when the voltage application interval is 10 seconds. In the figure, t _b (2.43 seconds) is the time required for decoloring, and t _c (0.65 seconds) is the time required for coloring.

Regarding the polymer obtained in Synthesis Example 1, the color change of the ITO electrode when a voltage of 0.0 V and +1.8 V was applied was visually observed (see FIG. 11A). A bright orange color was observed when 0.0 V was applied, and a slightly lighter green color was observed when +1.8 V was applied (each of which was clearer than the color of FIG. 9A).
FIG. 11B shows the light transmittance (%) of the same polymer in the cast state and at the time of 0.0 V and when +1.8 V is applied, and the wavelength (nm) on the vertical axis. Is shown on the horizontal axis. FIG. 11 (c) shows the change over time in the light transmittance (%) of the polymer when the insertion interval is changed to 10 seconds, 5 seconds or 2 seconds and a voltage is repeatedly applied (electrochemical response). Indicates. Unlike FIG. 9 (c), the electrochemical response of this polymer did not decrease even when the voltage application interval was changed from 10 seconds to 5 seconds.
FIG. 12 (a) shows the change with time (electrochemical response) of the light transmittance (%) of this polymer from 0 to 100 seconds when the voltage application interval is 10 seconds. Similarly, FIG. 12B shows the time-dependent change (electrochemical responsiveness) of the light transmittance (%) of this polymer up to 20 to 40 seconds when the voltage application interval is 10 seconds. In the figure, t _b (2.38 seconds) is the time required for decoloring, and t _c (1.18 seconds) is the time required for coloring. It was found that the peak sharpness, that is, the response speed was faster than those in FIGS. 10 (a) and 10 (b).
FIG. 12 (c) shows the electrochemical response in the form of permeability loss (%) with respect to current (A) for each sample of the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example. A control is shown. Also from this figure, it is proved that the polymer obtained in Synthesis Example 1 has an excellent electrochemical response.

For the polymer obtained in Synthesis Example 1 and the polymer obtained in Comparative Synthesis Example, voltages +1.8 V and 0 V were applied at intervals of 5 seconds, electrolyte solution 0.1 M LiClO ₄ / ACN, ITO working area 1.5 cm The following table shows the electrochromic characteristics measured under the conditions of × 1.5 cm. In particular, regarding the contrast ΔT, the polymer obtained in the comparative synthesis example was 67.73%, whereas the polymer obtained in the synthesis example 1 was 81.21%, and the coloring efficiency η for the polymer obtained in Comparative synthesis example whereas there was a 318.6cm ² / C, the polymer obtained in synthesis example 1 it is noted that was 379.3cm ² / C. The results of these characteristics are considered to demonstrate that the polymer obtained in Synthesis Example 1 has superior electrochromic characteristics due to the higher structural regularity.

The results of measuring the UV-Vis spectrum of the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example under the conditions of solvent methanol and a concentration of 25 μM are shown in FIG. It is shown in FIG. The polymers and oligomers obtained in Synthesis Examples 1 to 4 showed sharper and higher absorbance peaks in charge transfer absorption near 510 nm than the polymers obtained in Comparative Synthesis Examples.
The results of measuring the UV-Vis spectrum of the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example under the conditions of solvent DMSO and concentration of 25 μM are shown in FIG. 14 shows. The polymers and oligomers obtained in Synthesis Examples 1 to 4 showed sharper and higher absorbance peaks in charge transfer absorption near 520 nm than the polymers obtained in Comparative Synthesis Examples.
Regarding the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, the conditions of solvent methanol, concentration 25 μM, λ _ex = 310 nm, and solvent methanol, concentration 25 μM , Λ _ex = 515 nm The results of measuring the photoluminescence spectrum are shown in FIGS. 15 (a) and 15 (b). Under the latter conditions, the emission intensity of the oligomers obtained in Synthesis Examples 2 to 4 was significantly higher than that of the polymer obtained in the Comparative Synthesis Example.
Regarding the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, the conditions of solvent DMSO, concentration 25 μM, λ _ex = 310 nm, and solvent DMSO, concentration 25 μM , Λ _ex = 510 nm The results of measuring the photoluminescence spectrum are shown in FIGS. 16 (a) and 16 (b). Under the latter conditions, the emission intensity of the oligomers obtained in Synthesis Examples 2 to 4 was significantly higher than that of the polymer obtained in the Comparative Synthesis Example.
For the polymer obtained in Synthesis Example 1, the oligomer obtained in Synthesis Examples 2 to 4, and the polymer obtained in Comparative Synthesis Example, TGA (thermogravimetric analysis) was performed at a scanning speed of 10 ° C./min and under conditions of nitrogen. The results are shown in FIG. The polymer obtained in Synthesis Example 1 and the oligomers obtained in Synthesis Examples 2 to 3 have higher structural regularity and fewer impurities than the polymer obtained in Comparative Synthesis Example, so that the weight loss (%) increases. It is thought. On the other hand, since the oligomer obtained in Synthesis Example 4 is a monomer and has a relatively low molecular weight, the weight loss is small.
FIG. 18 shows the results of X-ray diffraction performed on the polymer obtained in Synthesis Example 1 and the oligomers obtained in Synthesis Examples 2 to 4 under the conditions of a scanning speed of 0.02 / step and CuKα.

For the monomer oligomer obtained in Synthesis Example 4, reference numerals of each hydrogen relating to NMR measurement are shown in FIG. 19, and for this monomer oligomer, ¹ H-NMR is obtained under the conditions of solvent CD ₃ OD, frequency 300 MHz, and room temperature. The result of measuring (COSY-NMR) is shown in FIG. From this result, it was found that a desired monomer oligomer having a high degree of structural regularity was obtained.
For the pentameric oligomer obtained in Synthesis Example 3, reference numerals of each hydrogen relating to NMR measurement, and the results of ¹ H-NMR measurement of this oligomer under the conditions of solvent CD ₃ OD, frequency 300 MHz, room temperature 21. From this result, it was found that a desired pentamer oligomer having a high degree of structural regularity was obtained.
For the 10-mer oligomer obtained in Synthesis Example 2, the reference numerals of each hydrogen relating to NMR measurement, and the results of ¹ H-NMR measurement of this oligomer under the conditions of solvent CD ₃ OD, frequency 300 MHz, room temperature 22 shows. Moreover, the COSY-NMR measurement result about this oligomer is shown in FIG. 23 with the reference sign of each hydrogen. From this result, it was found that a desired 10-mer oligomer having a high degree of structural regularity was obtained.
The NMR measurement results for the 10-mer oligomer, pentamer oligomer, and monomer oligomer obtained in Synthesis Examples 2 to 4 are also shown in FIG.
FIG. 25 shows the result of ¹ H-NMR measurement of the polymer obtained in Synthesis Example 1 under the conditions of each hydrogen reference code for NMR measurement and solvent CD ₃ OD, frequency 300 MHz, room temperature. (Same as the NMR measurement result in the upper part of FIG. 7). From this result, it was found that a desired polymer having a high degree of structural regularity was obtained.

According to the production method of the present invention, it is possible to easily supply a large chemical energy necessary for complex formation by an internal heating method using microwaves, so that the reaction time is short and the reaction conditions are mild. Since the reaction procedure is also simple, at least one ion of a transition metal other than Ru and / or a lanthanoid metal is used, and 4 ′, 4 ′ ′ ′-(1,4-phenylene) bis ( Even when any one of at least one organic ligand other than 2,2 ′: 6 ′, 2 ′ ′-terpyridine) is used, as described above, simply and efficiently without excessive trial and error. The metallo supramolecular polymer having a high structural regularity with respect to a desired structure at the same time that the invention can be carried out ("Providing a novel production method" which is one of the problems can be solved) Composition containing It is expected to be obtained. As a result, it is considered that a good electrochromic device can be efficiently obtained using such a metallo-supramolecular polymer-containing composition having a high structural regularity.

Claims (17)

A method for producing a metallo-supramolecular polymer-containing composition having improved structural regularity,
At least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are reacted by internal heating by microwave irradiation, and both are alternately Forming a coordinated metallo-supramolecular polymer.   The at least one organic ligand includes an organic ligand having any one or more of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and derivatives thereof. The manufacturing method of the metallo supramolecular polymer containing composition of description.   At least one of the transition metal and / or lanthanoid metal includes a metal selected from iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osnium, iridium, platinum, gold, europium and terbium. The manufacturing method of the metallo supramolecular polymer containing composition of Claim 1 or 2.   The molar ratio of at least one organic ligand to be subjected to an internal heating reaction by microwave irradiation to at least one ion of a transition metal and / or a lanthanoid metal is 1: 1 to 2: 1. The manufacturing method of the metallo supramolecular polymer containing composition of any one of Claims 1-3. The metallo-supramolecular polymer-containing composition according to any one of claims 1 to 4, wherein the at least one organic ligand includes an organic ligand having a structure represented by at least one of the following formulas: Manufacturing method:





Here, R is a spacer containing a carbon atom and a hydrogen atom, or a spacer that directly connects any one of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, and an acetylacetonate group, and R ¹ , R ² , R ³ and R ⁴ are all the same, different or partly the same hydrogen atom, aryl group or alkyl group.   The method for producing a metallo-supramolecular polymer-containing composition according to any one of claims 1 to 5, wherein the internal heating reaction by microwave irradiation is performed at a temperature of 150 ° C or higher. The method for producing a metallo-supramolecular polymer-containing composition according to any one of claims 1 to 6, wherein the metallo-supramolecular polymer-containing composition contains any of oligomers represented by the following structural formulas.
A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
For this composition, the absorption signal A due to each proton of the organic ligand at the polymer end in ¹ H-NMR measured under the conditions of solvent CD ₃ OD, predetermined concentration, frequency 300 MHz, and room temperature is the same organic. A metallo-supramolecular polymer-containing composition for reference obtained by performing a reaction until the consumption of raw materials reaches a steady state by external heating at a predetermined temperature required for complex formation, using the same metal ion as the ligand Absorption signal A corresponding to absorption signal A due to each proton of the organic terminal organic ligand in ¹ H-NMR measured under the conditions of solvent CD ₃ OD, same predetermined concentration, frequency 300 MHz, room temperature The above metallo-supramolecular polymer with enhanced structural regularity indicated by a state of less broadening compared to ' Containing composition. A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
Electrochromic properties of this composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm Contrast ΔT (%) and / or coloring efficiency η (cm ² / C) uses the same organic ligand and the same metal ion, and the consumption of raw materials is increased by external heating at a predetermined temperature required for complex formation. For the reference metallo-supramolecular polymer-containing composition obtained by carrying out the reaction until reaching a steady state, applied voltage +1.8 V and 0 V, at intervals of 5 seconds, electrolyte solution 0.1 M LiClO ₄ / ACN, ITO electrode Electrochromic contrast ΔT ′ (%) and / or coloring efficiency η ′ (c) measured in the upper working area 1.5 cm × 1.5 cm ^{2 /} C) with enhanced structural regularity represented by the state that larger than that, the metallo supramolecular polymer-containing composition. A metallo-supramolecular polymer-containing composition in which at least one organic ligand having a plurality of metal coordination sites and at least one ion of a transition metal and / or a lanthanoid metal are alternately coordinated. And
Electrochromic properties of this composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm The metallo-supramolecular polymer-containing composition having a contrast ΔT (%) of 70% or more and / or a coloring efficiency η (cm ² / C) of 320 cm ² / C or more. Electrochromic properties of the above composition measured at applied voltages +1.8 V and 0 V, 5 sec interval, 0.1 M LiClO ₄ / ACN electrolyte solution, working area on ITO electrode 1.5 cm × 1.5 cm The metallo-supramolecular polymer-containing composition according to claim 9, wherein the contrast ΔT (%) is 70% or more and / or the coloring efficiency η (cm ² / C) is 320 cm ² / C or more.   The at least one organic ligand includes an organic ligand having any one or more of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, an acetylacetonate group, and derivatives thereof. 11. The metallo-supramolecular polymer-containing composition according to any one of 11 above.   At least one of the transition metal and / or lanthanoid metal includes a metal selected from iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osnium, iridium, platinum, gold, europium and terbium. The metallo supramolecular polymer-containing composition according to any one of claims 8 to 12.   14. The molar ratio of at least one organic ligand to at least one ion of a transition metal and / or lanthanoid metal is 1: 1 to 2: 1. Metallo supramolecular polymer-containing composition as described in 1. The metallo supramolecular polymer-containing composition according to any one of claims 8 to 14, comprising a metallo supramolecular polymer having a structure represented by the following at least one formula and a counter anion:





Here, R is a spacer containing a carbon atom and a hydrogen atom, or a spacer that directly connects any one of a terpyridyl group, a bipyridyl group, a pyridyl group, a phenanthrolyl group, and an acetylacetonate group, and R ¹ , R ² , R ³ , R ⁴ are all the same, all different, or partly the same hydrogen atom, aryl group or alkyl group, and M is one or more of transition metal and / or lanthanoid metal N is an integer of 2 or more indicating the degree of polymerization, and counter anions are halide ions such as chloride ions, hydroxide ions, acetate ions, perchlorate ions, carbonate ions, four ions. Boron fluoride ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, (CF ₃ SO ₂ ) ₂ N ion , Polyoxymetalates, or combinations thereof. The metallo supramolecular polymer-containing composition according to any one of claims 8 to 15, comprising any oligomer represented by the following structural formula.
The metallo supramolecular polymer according to any one of claims 8 to 16, wherein the metallo supramolecular polymer is located between the first transparent electrode, the second transparent electrode, and the first transparent electrode and the second transparent electrode. An electrochromic device comprising the containing composition.