HK1165953B - Heterocyclical chromophore architectures - Google Patents

Description

Heterocyclic chromophore architectures

This application is a divisional application of the invention patent application entitled "heterocyclic chromophore structure" filed on 25.4.2007 with application No. 200580036669.5.

Background

Polymeric electro-optic (EO) materials have shown tremendous potential in a wide range of system and device core applications including phased array radar, satellite and fiber optic communications, cable television (CATV), optical gyroscopes for aviation and missile guidance, Electronic Countermeasure (ECM) systems, backplane interconnects for high speed computing, ultrafast analog-to-digital conversion, mine detection, radio frequency photonics, spatial light modulation, and all-optical (light-to-light) signal processing.

Nonlinear optical materials are capable of changing their first, second, third and higher order polarizabilities (two-photon absorption) in the presence of an externally applied electric field or incident light. In telecommunications applications, the second order polarizability (hyperpolarizability or β) and the third order polarizability (second hyperpolarizability or γ) are currently of great interest. The hyperpolarizability is related to the change in the refractive index of the NLO material in response to an applied electric field. The second order hyperpolarizability is related to the change in refractive index in response to photon absorption and thus to all optical signal processing. A more complete discussion of Nonlinear optical materials can be found in D.S. Chemla and J.Zys, Nonlinear optical properties of organic molecules and crystals (Nonlinear optical properties of organic molecules and crystals), Academic Press, 1987 and K.

A chromophore-Disperse Red (DR), originally evaluated by Bell laboratories in the sixties of the twentieth century because of its outstanding NLO properties, shows an electro-optical coefficient μ β of 580 × 10^-48Current molecular design, including FTC, CLD and GLD, showed μ β values exceeding 10,000 × 10^-48esu. See, Dalton et al, "New Class of Organic Chromophores with High Hyperpolarizability and methods for their synthesis" (New Class of High Hyperpolizability Organic Chromophores and Processes for synthesizing the Same) ", WO 00/09613.

However, the micro-molecular hyperpolarizability (β) is converted into a macro-material hyperpolarizability (X)⁽²⁾) Great difficulties are encountered. The molecular subcomponents (chromophores) must be integrated into the NLO material, which shows: (i) highly macroscopic non-linearity; and (ii) sufficient time, thermal, chemical and photochemical stability. Simultaneous resolution of these dual problems is considered to be a final impediment when EO polymers are widely commercialized in many governments and commercial facilities and systems.

High material hyperpolarizability (X)⁽²⁾) Is limited by the poor interaction properties of NLO chromophores. Commercially viable materials must combine chromophores with a desired molecular moment that is statistically oriented along a single material axis. To achieve this configuration, the charge transfer (dipole) nature of NLO chromophores is typically exploited by applying an external electric field during material processing that creates local low energy conditions that favor the non-centrosymmetric order. Unfortunately, at even moderate chromophore densities, the molecules form multi-molecular dipolar-bound (centrosymmetric) aggregates that cannot be broken down by practical electric field energy. As a result, NLO material performance tends to decrease dramatically after about 20-30% weight loading. One possible solution to this situation is to prepare higher performance chromophores that can produce the desired hyperpolarizing properties at very low molecular concentrations。

Attempts to make higher performance NLO chromophores have largely failed due to the nature of the molecular structures employed throughout the scientific community. Currently, all high performance chromophores (e.g., CLD, FTC, GLD, etc.) incorporate a "naked" chain of permanent alternating mono-di pi-conjugated covalent bonds. Researchers such as doctor sethmader have provided a profound and detailed study of the quantum mechanical effects of this "bond alternation" system, which is invaluable to our current understanding of the origin of NLO phenomena, and in turn led the direction of effort in modern chemical engineering. While increasing the length of these chains generally improves NLO properties, there is little or no improvement in material properties once these chains exceed about 2 nm. This is assumed to be due primarily to: (i) bending and rotation of the conjugated atom chain, which destroys the pi-conduction of the system, thus reducing the resulting NLO properties; and (ii) instability of this macromolecular system towards orientation within the material matrix due to environmental steric damping during poling. Therefore, future chromophore architectures must exhibit two important properties: (i) high rigidity, and (ii) a smaller conjugated system that concentrates NLO activity within a more compact molecular size.

Long-term thermal, chemical and photochemical stability are the only most important issues in constructing an effective NLO material. Material instability is largely a result of three factors: (i) increased sensitivity to nucleophilic attack by NLO chromophores, either due to molecular and/or intramolecular (CT) charge transfer or (quasi-) polarization, or due to high electric field poling processes at molecular and intramolecular resonance energies; (ii) this facilitates the reorientation of the molecule over time to a performance-detrimental centrosymmetric configuration due to the molecular motion of the light-induced cis-trans isomerization; and (iii) incorporation of NLO chromophores within the bulk crosslinked polymer matrix is extremely difficult due to the inherent reactivity of the naked alternating linkage chromophore structure. Thus, future chromophore architectures: (i) must exhibit improved CT and/or quasi-polar state stability; (ii) (ii) inability to incorporate structures that undergo photo-induced cis-trans isomerization; and (iii) must be highly resistant to polymerization processes by the total exclusion of possible naked alternating bonds.

The present invention seeks to meet these needs by innovating fully heterocyclic anti-aromatic chromophore designs. The heterocyclic systems described herein do not incorporate naked chains of alternating bonds that are prone to bending or rotation. The central anti-aromatic conductor "pulls" the molecule into the quasi-CT state; since both the aromatic and non-CT states are favorable low energy states, charge transfer and aromaticity within the molecular systems described herein balance each other in a competitive environment. This competing situation is known as CAPP engineering or Charge-aromatic Push-Pull (Charge-aromatic Push-Pull). As a result, the incorporation of an anti-aromatic system dramatically improves the conductive properties of the central pi-conjugated bridge, providing smaller molecular lengths with significantly stronger NLO properties. Since all of the systems described herein are aromatic in their CT state and quasi-aromatic in their intermediate quasi-polar state, this structure is expected to dramatically improve the polar stability. Furthermore, described herein are novel electron acceptor systems that are expected to significantly improve the excited state and quasi-CT delocalization, making the overall system less susceptible to nucleophilic attack. The heterocyclic nature of all the systems described herein prohibits the presence of light-induced cis-trans isomerization, which is suspected to be the cause of both material and molecular degradation. Finally, the present invention provides a color system that lacks naked alternating bonds that are reactive under polymerization conditions.

Summary of The Invention

The present invention relates to NLO chromophores of the form I, or acceptable salts thereof, useful for generating first, second, third and/or higher order polarizabilities:

formula I

Wherein:

(p) is 0 to 6;

independently at each occurrence is a covalent chemical bond;

X^1-4independently selected from C, N, O or S;

Z^1-4independently N, CH or CR; wherein R is as defined below.

D is an organic electron donating group with an electron affinity equal to or lower than the electron affinity of A. In the presence of¹In the case of D in two atomic positions X¹And X²To the rest of the molecule. In the absence of pi¹In the case of D in two atomic positions Z¹And C²To the rest of the molecule.

A is an organic electron accepting group having an electron affinity equal to or higher than that of D. In the presence of²In the case of (A) in two atomic positions X³And X⁴To the rest of the molecule. In the absence of pi²In the case of A in two atomic positions Z⁴And C³To the rest of the molecule.

π¹Comprising X¹And X²，π¹Absent or bound to atom pair Z¹And C²ToBridge of (a)¹At D and including C¹、C²、C³、C⁴、Z¹、Z²、Z³And Z⁴Provide electron conjugation between the anti-aromatic systems.

π²Comprising X³And X⁴，π²Absent or linking atom pair C³And Z⁴ToBridge of (a)²Providing an electronic conjugation between a and the anti-aromatic system.

R is independently selected from:

(i) a spacer system of formula II or an acceptable salt thereof:

formula II

Wherein:

R₃is C₆-C₁₀Aryl radical, C₆-C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆-C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; and the above R³The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₁and R₂Independently selected from the group consisting of₃The substituents as provided in the definition of (A), (CH)₂)_t(C₆-C₁₀Aryl) or (CH)₂)_t(4-to 10-membered heterocyclic group), t is an integer of 0 to 5, and the above-mentioned R₁And R₂The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₄independently selected from the group consisting of₃A substituent, chemical bond (-), or hydrogen provided in the definition of (1);

Q¹、Q²and Q⁴Each independently selected from hydrogen, halogen, C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、-NR⁶C(O)OR⁵、-NR⁶SO₂R⁵、-SO₂NR⁵R⁶、-NR⁶C(O)R⁵、-C(O)NR⁵R⁶、-NR⁵R⁶、-S(O)_jR⁷Wherein j is an integer from 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、-(CH₂)_t(C₆-C₁₀Aryl), -SO₂(CH₂)_t(C₆-C₁₀Aryl), -S (CH)₂)_t(C₆-C₁₀Aryl), -O (CH)₂)_t(C₆-C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; with the proviso that when R⁴When is hydrogen Q⁴Is absent; said alkyl group optionally containing 1 or 2 substituents selected from O, S and-N (R)⁶) -said aryl and heterocyclic Q groups are optionally fused to C₆-C₁₀Aryl radical, C₅-C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; optionally substituted with an oxo (═ O) moiety for 1 or 2 carbon atoms in the above heterocyclic moiety; and the alkyl, aryl and heterocyclic moieties of the aforementioned Q groups are optionally substituted with 1 to 3 substituents independently selected from the group consisting of: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶SO₂R⁵、-SO₂NR⁵R⁶、-NR⁶C(O)R⁵、-C(O)NR⁵R⁶、-NR⁵R⁶、-(CR⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5, -OR⁵And R⁵The substituents listed in the definitions of (1);

R⁵each independently selected from H, C₁-C₁₀Alkyl, - (CH)₂)_t(C₆-C₁₀Aryl) and- (CH)₂)_t(4-10 membered heterocyclyl), wherein t is an integer from 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) -said aryl and heterocycle R⁵The radicals being optionally fused to C₆-C₁₀Aryl radical, C₅-C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; and the above R⁵Substituents, other than H, optionallySubstituted with 1-3 substituents independently selected from the group consisting of: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶C(O)R⁷、-C(O)NR⁶R⁷、-NR⁶R⁷Hydroxy, C₁-C₆Alkyl and C₁-C₆An alkoxy group;

R⁶and R⁷Each independently is H or C₁-C₆An alkyl group;

t, U and V are each independently selected from C (carbon), O (oxygen), N (nitrogen) and S (sulfur), and are included in R³Performing the following steps;

t, U and V are directly adjacent to each other; and

w is R³Is not a hydrogen atom and is not T, U or V; or

(ii) Hydrogen, halogen, C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、-NR⁶C(O)OR⁵、-NR⁶SO₂R⁵、-SO₂NR⁵R⁶、-NR⁶C(O)R⁵、-C(O)NR⁵R⁶、-NR⁵R⁶、-S(O)_jR⁷Wherein j is an integer from 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、-(CH₂)_t(C₆-C₁₀Aryl), -SO₂(CH₂)_t(C₆-C₁₀Aryl), -S (CH)₂)_t(C₆-C₁₀Aryl), -O (CH)₂)_t(C₆-C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) A hetero moiety of (A) wherein R is⁵、R⁶And R⁷As defined above.

Another embodiment of the invention relates to compounds of the formula I, in which¹C of conjugated bridges with anti-aromatic systems²And Z¹Attached in a manner selected from:

wherein R is as defined above.

Another embodiment of the invention relates to compounds of formula I wherein the electron donating group (D) is selected from the group consisting of¹X of conjugated bridges¹And X²Attached in a manner selected from:

and wherein R is as defined above.

Another embodiment of the invention relates to compounds of the formula I, in which²C of conjugated bridges with anti-aromatic systems³And Z⁴Attached in a manner selected from:

wherein R is as defined above.

Another embodiment of the invention relates to compounds of the formula I, in which the electron-accepting group (A) is bound to π²X of conjugated bridges³And X⁴Attached in a manner selected from:

wherein R is independently at each occurrence as defined above; and Acc is selected from CN, NO₂、SO₂R, and 0 < n < 5.

Another non-limiting example of the present invention includes the following chromophores:

wherein R is independently at each occurrence as defined above.

Another non-limiting example of the present invention includes the following chromophores:

wherein R is independently at each occurrence as defined above.

In the present invention, the term "nonlinear optical chromophore" (NLOC) is defined as a molecule or portion of a molecule that produces a nonlinear optical effect when irradiated with light. The chromophore is any molecular unit whose interaction with light results in a nonlinear optical effect. The desired effect may occur at resonant or non-resonant wavelengths. The activity of a particular chromophore in a nonlinear optical material is expressed as its hyperpolarizability, which is directly related to the molecular dipole moment of the chromophore.

In the present invention, the term "halogen" includes fluorine, chlorine, bromine or iodine unless otherwise specified. Preferred halogen groups are fluorine, chlorine and bromine.

The term "alkyl" as used herein, unless otherwise specified, includes saturated monovalent hydrocarbon radicals having straight, cyclic, or branched moieties. It is understood that for cyclic moieties, at least three carbon atoms are required in the alkyl group.

The term "alkenyl", as used herein, unless otherwise specified, includes monovalent hydrocarbon radicals having at least one carbon-carbon double bond, and also having straight, cyclic, or branched moieties as provided above in the definition of "alkyl".

The term "alkynyl", as used herein, unless otherwise specified, includes monovalent hydrocarbon radicals having at least one carbon-carbon triple bond and also having straight, cyclic, or branched moieties as provided above in the definition of "alkyl".

The term "alkoxy" as used herein, unless otherwise indicated, includes O-alkyl, wherein "alkyl" is as defined above.

The term "aryl" as used herein, unless otherwise specified, includes organic groups derived from aromatic hydrocarbons by removal of one hydrogen, such as phenyl or naphthyl.

As used herein, unless otherwise indicated, the term "heteroaryl" includes organic radicals derived from a heteroarene ring by removal of one hydrogen atom from a carbon atom, which contains one or more heteroatoms independently selected from O, S and N. Heteroaryl groups must have at least 5 atoms in their ring system and are optionally substituted by 0-2 halogens, trifluoromethyl, C₁-C₆Alkoxy radical, C₁-C₆Alkyl or nitro is independently substituted.

The term "4-10 membered heterocyclyl" as used herein, unless otherwise indicated, includes aromatic and non-aromatic heterocyclic groups containing one or more heteroatoms selected from O, S and N, respectively, wherein each heterocyclic group has 4-10 atoms in its ring system. Non-aromatic heterocyclic groups included in the ringThere are only 4 atoms in the system, but an aromatic heterocyclic group must have at least 5 atoms in its ring system. An example of a 4-membered heterocyclic group is azetidinyl (derived from azetidine). An example of a 5-membered heterocyclic group is thiazolyl, and an example of a 10-membered heterocyclic group is quinolinyl. Examples of non-aromatic heterocyclic groups are pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thienylalkyl, piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxepanyl (oxepanyl), thiepanyl (thiepanyl), oxazepinyl (oxazepinyl), diazacycloyl (diazepinyl), thiazepinyl (thiazepinyl), 1, 2, 3, 6-tetrahydropyridinyl, 2-pyrrolinyl, 3-pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1, 3-dioxolanyl, pyrazolinyl, dithianyl, dithiopentyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinyl, dihydropyranyl, dihydrofuranyl, thianyl, thiapanyl, thianyl, Imidazolinyl, imidazolidinyl, 3-azabicyclo [3.1.0]Hexane radical, 3-azabicyclo [4.1.0 ]]A heptylalkyl group,³H-indolyl and quinolizinyl. Examples of aromatic heterocyclic groups are pyridyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolyl, isoquinolyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, 2, 3-naphthyridinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, oxadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, 1, 5-naphthyridinyl, and furylpyridinyl (furylpyridinyl). The above groups derived from the above listed compounds may be C-linked or N-linked, where such is possible. For example, a group derived from pyrrole may be pyrrol-1-yl (N-linked) or pyrrol-3-yl (C-linked).

Unless otherwise indicated, the term "saturated cyclic group" as used herein includes non-aromatic, fully saturated cyclic moieties in which alkyl is as defined above.

The phrase "acceptable salts" as used herein, unless otherwise specified, includes salts of acidic or basic groups that may be present in the compounds of the present invention. The compounds of the present invention which are basic in nature are capable of forming a wide variety of salts with a wide variety of inorganic and organic acids. The acids which can be used to prepare the pharmaceutically acceptable acid addition salts of such basic compounds of the present invention are those which form non-toxic acid addition salts, the non-toxic acid addition salts are i.e. salts containing pharmacologically acceptable anions such as hydrochloride, hydrobromide, hydroiodide, nitrate, sulphate, bisulphate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate, maleate, gentisate, fumarate, gluconate, glucarate (glucaronate), saccharate, formate, benzoate, glutamate, methanesulphonate, ethanesulphonate, benzenesulphonate, p-toluenesulphonate and pamoate [ i.e. 1, 1' -methylene-bis- (2-hydroxy-3-naphthoate) ].

Those compounds of the invention that are acidic in nature are capable of forming base salts with a variety of pharmacologically acceptable cations. Examples of such salts include alkali metal or alkaline earth metal salts, particularly sodium and potassium salts.

The term "solvate" as used herein includes a compound of the invention or a salt thereof, which further includes a stoichiometric or non-stoichiometric amount of a solvent bound by non-covalent intermolecular forces.

The term "hydrate" as used herein refers to a compound of the invention or a salt thereof, which further comprises a stoichiometric or non-stoichiometric amount of water bound by non-covalent intermolecular forces.

Certain compounds of the invention may have asymmetric centers and thus occur in different enantiomeric forms. The present invention relates to the use of all optical isomers and stereoisomers of the compounds of the invention and mixtures thereof. The compounds of the present invention may also occur as tautomers. The present invention relates to the use of all such tautomers and mixtures thereof.

The invention also includes isotopically-labelled compounds, and commercially acceptable salts thereof, which are identical to those recited in formulas I and II, except for the fact that: one or more atoms are replaced by an atom having an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Examples of isotopes that can be incorporated into the compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, sulfur, fluorine and chlorine, such as²H、³H、¹³C、¹⁴C、¹⁵N、¹⁸O、¹⁷O、³⁵S、¹⁸F and³⁶and (4) Cl. Compounds of the present invention that contain the aforementioned isotopes and/or other isotopes of other atoms, as well as commercially acceptable salts of such compounds, are within the scope of the present invention. Certain isotopically-labelled compounds of the present invention, for example, in which a radioactive isotope such as³H and¹⁴c, are useful in drug and/or substrate tissue distribution assays. Tritiated isotopes are readily prepared and detectable³H and carbon-14 i.e¹⁴C is particularly preferred. In addition, heavier isotopes such as deuterium are used, i.e.²Substitution of H, due to its greater stability, may provide certain advantages. Isotopically labeled compounds of formula I of the present invention can be prepared by carrying out the procedures disclosed in the schemes and/or in the examples and preparations below, by substituting a readily available isotopically labeled reagent for a non-isotopically labeled reagent.

The patents, patent applications, published international applications and scientific publications cited in this patent application are all incorporated herein by reference in their entirety.

Detailed Description

The compounds of formula I are useful structures for producing NLO effects.

First order hyperpolarizability (β) is one of the most common and useful NLO properties. Higher order hyperpolarizabilities are useful in other applications such as all-optical (light-to-light conversion) applications. To determine whether a material, such as a compound or polymer, includes a nonlinear optical chromophore with first order nonpolar properties, the following experiment may be performed. First, a material in the form of a thin film is placed in an electric field to align the dipoles. This may be done by interposing a film of material, such as an Indium Tin Oxide (ITO) substrate, a gold film or a silver film, between the electrodes.

To generate a poling electric field, an electric potential is then applied to the electrodes while the material is heated to near its glass transition (Tg) temperature. After a suitable period of time, the temperature is gradually reduced while maintaining the poling electric field. Alternatively, the material may be poled by corona poling, in which charged needles at an appropriate distance from the material film provide the poling field. In both cases, the dipoles in the material tend to align with the electric field.

The nonlinear optical properties of the poled materials were then tested as follows. Polarized light, often from a laser, is passed through the poled material, then through a polarization filter, and to a light intensity detector. The material incorporates a nonlinear optical chromophore and has an electro-optically variable refractive index if the intensity of light received by the detector varies with the potential applied to the electrodes. A more detailed discussion of techniques for Measuring the Electro-optical Constants of formed polar films incorporating Nonlinear optical chromophores can be found in Chia-ChiTeng, Measuring the Electro-Optic Constants of polarized films, Nonlinear Optics of Organic Molecules and polymers (Measuring Electro-optical Constants of a polarized Film, Nonlinear Optics of Organic Molecules and polymers), Chp.7, 447-49(Hari Singh Nalwa & sezo Miyaeds., 1997), the disclosure or definition of which is incorporated herein by reference in its entirety, except that in the case of any definitions of disclosure that are inconsistent with the present application, the disclosure or definition herein should be considered to be valid.

The relationship between the change in applied potential and the change in refractive index of the material can be expressed as its EO coefficient r₃₃. This effect is commonly referred to as the electro-optic or EO effect. Devices comprising materials that change their refractive index as a function of the applied potential are known as electro-optical (EO) devices.

Exemplary compounds of formula I may be prepared according to the following reaction scheme. R in the reaction schemes and discussions below is as defined above.

Another exemplary compound of formula I may be prepared according to the following reaction scheme. R in the reaction schemes and discussions below is as defined above.

Claims (10)

1. A nonlinear optical chromophore of the formula:

wherein each R is independently selected from:

(i) a group of formula II:

wherein:

R₃is C₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; and the above-mentioned R³The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₁and R₂Independently selected from C₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; (CH)₂)_t(C₆－C₁₀Aryl) or (CH)₂)_t(4-10-membered heterocyclic group), t is an integer of 0 to 5, and the above-mentioned R₁And R₂The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₄independently selected from the group consisting of optionally substituted with 1-3R⁵The following groups substituted with groups: c₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; chemical bond (-), or hydrogen;

each Q¹、Q²And Q⁴Independently selected from hydrogen, halogen, C₁－C₁₀Alkyl radical, C₂－C₁₀Alkenyl radical, C₂－C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、－NR⁶C(O)OR⁵、－NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－S(O)_jR⁷Wherein j is an integer of 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、－(CH₂)_t(C₆－C₁₀Aryl), -SO₂(CH₂)_t(C₆－C₁₀Aryl), -S (CH)₂)_t(C₆－C₁₀Aryl), -O (CH)₂)_t(C₆－C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; with the proviso that when R⁴When it is hydrogen, Q⁴Is absent; said alkyl group optionally containing 1 or 2 substituents selected from O, S and-N (R)⁶) -a hetero moiety of (a), said Q¹、Q²And Q⁴Aryl and heterocyclic moieties of (a) optionally fused to C₆－C₁₀Aryl radical, C₅－C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; optionally substituted with an oxo (═ O) moiety for 1 or 2 carbon atoms in the above heterocyclic moiety; and Q is¹、Q²And Q⁴The alkyl, aryl and heterocyclic moieties of (a) are optionally substituted with 1 to 3 substituents independently selected from the group consisting of: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－(CR⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5, -OR⁵And R⁵The substituents listed in the definitions of (1);

each R⁵Independently selected from H, C₁－C₁₀Alkyl, - (CH)₂)_t(C₆－C₁₀Aryl) and- (CH)₂)_t(4-10 membered heterocyclyl), wherein t is an integer from 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) -said hetero moiety of (A), said R⁵Aryl and heterocyclic part of the group being optionally fused to C₆－C₁₀Aryl radical, C₅－C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; and the above-mentioned R⁵Substituents, other than H, optionally substituted by 1-3 substituent substituents independently selected from the group consisting of: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶C(O)R⁷、－C(O)NR⁶R⁷、－NR⁶R⁷Hydroxy, C₁－C₆Alkyl and C₁－C₆An alkoxy group;

each R⁶And R⁷Independently is H or C₁－C₆An alkyl group;

t, U and V are each independently selected from C (carbon), O (oxygen), N (nitrogen) and S (sulfur), and are included in R³Performing the following steps;

t, U and V are directly adjacent to each other; and is

W is R³Is not a hydrogen atom and is not T, U or V; or

(ii) Hydrogen, halogen, C₁－C₁₀Alkyl radical, C₂－C₁₀Alkenyl radical, C₂－C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、－NR⁶C(O)OR⁵、－NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－S(O)_jR⁷Wherein j is an integer of 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、－(CH₂)_t(C₆－C₁₀Aryl), -SO₂(CH₂)_t(C₆－C₁₀Aryl), -S (CH)₂)_t(C₆－C₁₀Aryl), -O (CH)₂)_t(C₆－C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) A hetero moiety of (A) wherein R is⁵、R⁶And R⁷As defined above.

2. The nonlinear optical chromophore of claim 1, wherein each R represents C₆－C₁₀And (4) an aryl group.

3. The nonlinear optical chromophore of claim 1, wherein each R represents a branched C₁－C₁₀An alkyl group.

4. The nonlinear optical chromophore of claim 1, wherein each R represents C₁-C₁₀An alkyl group.

5. The nonlinear optical chromophore of claim 1, wherein each R represents-SO₂(CH₂)_t(C₆-C₁₀Aryl).

6. A nonlinear optical chromophore of the formula:

wherein each R is independently selected from:

(i) a group of formula II:

wherein:

R₃is C₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; and the above-mentioned R³The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₁and R₂Independently selected from C₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl radical4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; (CH)₂)_t(C₆－C₁₀Aryl) or (CH)₂)_t(4-10-membered heterocyclic group), t is an integer of 0 to 5, and the above-mentioned R₁And R₂The radical being optionally substituted by 1 to 3R⁵Substituted by groups;

R₄independently selected from the group consisting of optionally substituted with 1-3R⁵The following groups substituted with groups: c₆－C₁₀Aryl radical, C₆－C₁₀Heteroaryl, 4-to 10-membered heterocyclic group or C₆－C₁₀A saturated cyclic group; 1 or 2 carbon atoms in the above cyclic moiety are optionally substituted with an oxo (═ O) moiety; chemical bond (-), or hydrogen;

each Q¹、Q²And Q⁴Independently selected from hydrogen, halogen, C₁－C₁₀Alkyl radical, C₂－C₁₀Alkenyl radical, C₂－C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、－NR⁶C(O)OR⁵、－NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－S(O)_jR⁷Wherein j is an integer of 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、－(CH₂)_t(C₆－C₁₀Aryl), -SO₂(CH₂)_t(C₆－C₁₀Aryl), -S (CH)₂)_t(C₆－C₁₀Aryl), -O (CH)₂)_t(C₆－C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; with the proviso that when R⁴When it is hydrogen, Q⁴Is absent; said alkyl group optionally containing 1 or 2 substituents selected from O, S and-N (R)⁶) -a hetero moiety of (a), said Q¹、Q²And Q⁴Aryl and heterocyclic moieties of (a) optionally fused to C₆－C₁₀Aryl radical, C₅－C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; optionally substituted with an oxo (═ O) moiety for 1 or 2 carbon atoms in the above heterocyclic moiety; and Q is¹、Q²And Q⁴The alkyl, aryl and heterocyclic moieties of (a) are optionally substituted with 1 to 3 substituents independently selected from the group consisting of: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－(CR⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5, -OR⁵And R⁵The substituents listed in the definitions of (1);

each R⁵Independently selected from H, C₁－C₁₀Alkyl, - (CH)₂)_t(C₆－C₁₀Aryl) and- (CH)₂)_t(4-10 membered heterocyclyl), wherein t is an integer from 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) -said hetero moiety of (A), said R⁵Aryl and heterocyclic part of the group being optionally fused to C₆－C₁₀Aryl radical, C₅－C₈A saturated cyclic group or a 4-to 10-membered heterocyclic group; and the above-mentioned R⁵Substituents, other than H, are optionally substituted with 1-3 substituents independently selected from the following substituents: nitro, trifluoromethyl, trifluoromethoxy, azido, -NR⁶C(O)R⁷、－C(O)NR⁶R⁷、－NR⁶R⁷Hydroxy, C₁－C₆Alkyl and C₁－C₆An alkoxy group;

each R⁶And R⁷Independently is H or C₁－C₆An alkyl group;

t, U and V are each independently selected from C (carbon), O (oxygen), N (nitrogen) and S (sulfur), and are included in R³Performing the following steps;

t, U and V are directly adjacent to each other; and is

W is R³Is not a hydrogen atom and is not T, U or V; or

(ii) Hydrogen, halogen, C₁－C₁₀Alkyl radical, C₂－C₁₀Alkenyl radical, C₂－C₁₀Alkynyl, nitro, trifluoromethyl, trifluoromethoxy, azido, -OR⁵、－NR⁶C(O)OR⁵、－NR⁶SO₂R⁵、－SO₂NR⁵R⁶、－NR⁶C(O)R⁵、－C(O)NR⁵R⁶、－NR⁵R⁶、－S(O)_jR⁷Wherein j is an integer of 0 to 2, -NR⁵(CR⁶R⁷)_tOR⁶、－(CH₂)_t(C₆－C₁₀Aryl), -SO₂(CH₂)_t(C₆－C₁₀Aryl), -S (CH)₂)_t(C₆－C₁₀Aryl), -O (CH)₂)_t(C₆－C₁₀Aryl), - (CH)₂)_t(4-10-membered heterocyclic group) and- (CR)⁶R⁷)_mOR⁶Wherein m is an integer of 1 to 5 and t is an integer of 0 to 5; said alkyl group optionally comprising 1 or 2 substituents selected from O, S and-N (R)⁶) A hetero moiety of (A) wherein R is⁵、R⁶And R⁷As defined above.

7. The nonlinear optical chromophore of claim 6, wherein each R represents C₆－C₁₀And (4) an aryl group.

8. The nonlinear optical chromophore of claim 6, wherein each R represents a branched C₁－C₁₀An alkyl group.

9. The nonlinear optical chromophore of claim 6, wherein each R represents C₁-C₁₀An alkyl group.

10. The nonlinear optical chromophore of claim 6, wherein each R represents-SO₂(CH₂)_t(C₆-C₁₀Aryl).