CN1087744C - Ruthenium (II) polypyridine match and its preparing process - Google Patents
Ruthenium (II) polypyridine match and its preparing process Download PDFInfo
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- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 3
- 239000003446 ligand Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- -1 phenanthroline imidazole derivative Chemical class 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000012327 Ruthenium complex Substances 0.000 abstract description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- NHKTUSUPCAKVHT-UHFFFAOYSA-L 2-pyridin-2-ylpyridine;ruthenium(2+);dichloride;dihydrate Chemical compound O.O.Cl[Ru]Cl.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 NHKTUSUPCAKVHT-UHFFFAOYSA-L 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000005281 excited state Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000013494 PH determination Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- 239000007793 ph indicator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
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- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- NPVSJHHEHSZIGE-UHFFFAOYSA-N 3,3-dimethyl-6-pyridin-2-yl-4h-pyridine Chemical compound N1=CC(C)(C)CC=C1C1=CC=CC=N1 NPVSJHHEHSZIGE-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 238000005442 molecular electronic Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及发光pH传感器技术领域。钌(II)多吡啶配合物通式与结构如图所示：其制法是将二(2，2’-联吡啶)-二氯-二水合钌(II)(即Ru(bpy)2Cl2·2H2O)与含酚羟基的菲罗啉咪唑衍生物配体按摩尔比1∶1在溶剂水-乙醇(1∶1)中回流5小时，除去溶剂，经层析处理得到目标化合物。本发明的化合物是将邻烷氧基酚强电子给体共价键与钌配合物相连，通过分子内电子转移实现配合物的发射对pH的依赖。本发明的化合物的发射对pH变化高度敏感，为已报道的类似分子的10倍，可用于高灵敏度的pH发光传感器。
The invention relates to the technical field of luminescent pH sensors. The general formula and structure of ruthenium(II) polypyridine complexes are shown in the figure: the preparation method is to prepare bis(2,2'-bipyridine)-dichloro-ruthenium(II) dihydrate (i.e. Ru(bpy) 2 Cl 2.2H 2 O) and the phenanthroline imidazole derivative ligand containing phenolic hydroxyl group in a molar ratio of 1:1 were refluxed in the solvent water-ethanol (1:1) for 5 hours, the solvent was removed, and the target compound was obtained by chromatography . The compound of the invention links the o-alkoxyphenol strong electron donor covalently with the ruthenium complex, and realizes the dependence of the emission of the complex on pH through intramolecular electron transfer. The emission of the compound of the present invention is highly sensitive to pH changes, which is 10 times that of similar molecules reported, and can be used in highly sensitive pH luminescent sensors.
Description
本发明属于高灵敏度的pH传感技术领域，特别是属于钌(II)多吡啶配合物制备及其发光对pH的高度灵敏响应.The invention belongs to the technical field of high-sensitivity pH sensing, in particular to the preparation of ruthenium (II) polypyridine complex and its highly sensitive response of luminescence to pH.
传感器或敏感器(sensor)就是对某些性质或分析物发生响应的分子。通常，一个敏感器由一个分子识别组分及一个响应组分组成，前者具有在混合物中与特定物种相结合的能力，后者则能够在结合后立即产生一个与之相应的信号改变。受生物过程中自然复杂现象的启示，化学家们已产成功地合成了许多复杂的有机分子，如王冠醚，穴状配体，球烷，及杯芳烃等，这些分子能与特定的离子或分子螯合，它们是分子识别的基础。一般说来，王冠醚及其相关化合物与特定物种结合后本身不能产生具有识别性的物理性质改变，而这正是信号传输及敏感的基础。为了克服这种困难，新一代的主体分子被用于该领域，其主要是基于过渡金属配合物的发光传感器。这种发光无机离子传感器由三部分组成：(1)一个离子识别位置(2)对分析物发生结合响应的发光组分(3)识别位置及发光组分之间的化学连接。Sensors or sensors are molecules that respond to certain properties or analytes. Typically, a sensor consists of a molecular recognition component, which has the ability to bind to a specific species in a mixture, and a response component, which produces a corresponding signal change immediately after binding. Inspired by the natural complex phenomena in biological processes, chemists have successfully synthesized many complex organic molecules, such as crown ethers, cryptands, globanes, and calixarenes, which can be combined with specific ions or Molecular chelation, they are the basis of molecular recognition. Generally speaking, the combination of crown ether and its related compounds with specific species cannot produce recognizable physical property changes, which is the basis of signal transmission and sensitivity. To overcome this difficulty, a new generation of host molecules has been used in this field, which is mainly based on transition metal complexes for luminescent sensors. This luminescent inorganic ion sensor consists of three parts: (1) an ion recognition site (2) a luminescent component that responds to the analyte binding (3) a chemical link between the recognition site and the luminescent component.
尽管有许多发光过渡金属配合物，只有钌多吡啶配合物及铑三羰基α-二亚胺配合物已用于发光探针。这是由于它们的热及化学稳定性、水溶性、强的可见吸收、有效的发射及长寿命的激发态。而且由于它们的激发态是极性的，其激发态特性如发射量子效率，发射寿命及氧化还原势等在很大程度上会受到辅助配体，溶剂极性，及其他环境因素的影响。在光学传感器中常用的测量方法是吸收、发射或折射光谱，而发射技术具有内在的高灵敏度。由于发射波长总是长于入射波长，这样相对于零或近零背景读出信号是可能的，对于发射的扰动发射信号可以通过强度，强度比或寿命等形式来记录。过渡金属配合物做为发射探针有许多潜在优势，包括长的激发态寿命及高的发射量子产率。与典型的纳秒有机荧光探针相比，长的激发态寿命使得它们很容易测量，而且对无处不在的短寿命的有机发光物质提供了有效的时间区别。Although there are many luminescent transition metal complexes, only ruthenium polypyridine complexes and rhodium tricarbonyl α-diimine complexes have been used as luminescent probes. This is due to their thermal and chemical stability, water solubility, strong visible absorption, efficient emission, and long-lived excited states. And because their excited states are polar, their excited state properties such as emission quantum efficiency, emission lifetime, and redox potential are largely affected by auxiliary ligands, solvent polarity, and other environmental factors. Common measurement methods used in optical sensors are absorption, emission or refraction spectroscopy, with emission techniques inherently highly sensitive. Since the emission wavelength is always longer than the incident wavelength, it is possible to read out the signal relative to a zero or near-zero background. For emission perturbations, the emission signal can be recorded in terms of intensity, intensity ratio, or lifetime. Transition metal complexes have many potential advantages as emissive probes, including long excited state lifetimes and high emission quantum yields. Compared with typical nanosecond organic fluorescent probes, the long excited-state lifetimes make them easy to measure and provide effective temporal discrimination for ubiquitous short-lived organic luminescent species.
基态吸收随pH变化的物质早已用于pH的定量测定及pH指示剂。但吸收光谱一般是相当不敏感的也难用于远距离光纤及小的pH测定。在发射光谱上具有pH依赖的发光分子可用作灵敏的pH指示剂。这种离子(包括H+)控制发射不仅对生命科学中的离子敏感有意义而且对于构建分子电子器件同样具有重要意义。相当多的生命现象都是在一定的pH条件下进行的，正常细胞和肿瘤细胞中的pH有明显的差别。细胞中pH值的快速准确测定对于肿瘤诊断也是很有意义的，然而传统的pH计是无能为力的。高灵敏度微型能远距离测定的pH发光传感器在这方面应该具有潜在的应用。尽管这种pH发光传感器还处于早期研究阶段，文献报道还不多见，其前景是很好的。1992年格里格首次在英国化学会志上(R.Grigg，E.D.J.A.Norgert，J.Chem.Soc.Chem.Communication.1992，1300.)报道了基于联吡啶钌配合物的发光pH传感器，它们是联吡啶钌通过亚甲基与各种胺相连，通过胺的质子化与去质子化来影响配合物的发射而产生pH敏感，配合物的发射性质随pH的变化而变化。1994年格里格又在英国化学会志(R.Grigg，J.M.Holmes，S.K.Jones，E.D.J.A.Norgert，J.Chem.Soc.Chem.Communication.1994，185.)报道以联吡啶钌为发光单元，杯芳烃作为酸碱敏感单元的发光pH传感器，研究了这些化合物的发射随pH变化的特性。尽管报道的这些分子的发射性质具有pH敏感特性，但其pH敏感的程度还不是很高，在其pH敏感范围内的发射强度变化约4-5倍。且化合物的合成复杂，特别是配体杯芳烃2，2-联吡啶及5，5-二甲基联吡啶不易合成。Substances whose ground state absorption varies with pH have long been used in the quantitative determination of pH and as pH indicators. However, absorption spectroscopy is generally quite insensitive and difficult to use for long-distance optical fibers and small pH measurements. Luminescent molecules with pH dependence in emission spectra can be used as sensitive pH indicators. This ion (including H + ) controlled emission is not only meaningful for ion sensitivity in life sciences but also important for the construction of molecular electronic devices. Quite a number of life phenomena are carried out under a certain pH condition, and there are obvious differences in the pH between normal cells and tumor cells. The rapid and accurate determination of pH value in cells is also very meaningful for tumor diagnosis, but the traditional pH meter is powerless. High-sensitivity miniature pH luminescent sensors capable of remote measurement should have potential applications in this regard. Although this pH luminescent sensor is still in the early research stage, and there are not many reports in the literature, its prospect is very good. In 1992, Grigg reported the luminescent pH sensor based on bipyridyl ruthenium complexes for the first time in the Journal of the British Chemical Society (R.Grigg, EDJANorgert, J.Chem.Soc.Chem.Communication.1992, 1300.). Ruthenium pyridine is connected to various amines through methylene, and the protonation and deprotonation of the amines affect the emission of the complex to produce pH sensitivity. The emission properties of the complex change with the change of pH. In 1994, Grigg reported in the Journal of the British Chemical Society (R.Grigg, JMHolmes, SK Jones, EDJANorgert, J.Chem.Soc.Chem.Communication.1994, 185.) that bipyridyl ruthenium was used as the light-emitting unit, and calixarene was used as the acid Luminescent pH sensors with base-sensitive cells, the pH-dependent emission properties of these compounds were investigated. Although the reported emission properties of these molecules are pH sensitive, the degree of pH sensitivity is not very high, and the emission intensity varies by about 4-5 times in the pH sensitive range. Moreover, the synthesis of the compound is complicated, especially the ligands calixarene 2,2-bipyridine and 5,5-dimethylbipyridine are difficult to synthesize.
本发明的目的在于克服上述缺点，提供了一种结构简单的钌(II)多吡啶配合物及其制备方法。本发明的钌(II)多吡啶配合物，其配合离子对应于下列通式：本发明的钌多吡啶配合物的制备方法按如下步骤进行：The object of the present invention is to overcome above-mentioned shortcoming, provide a kind of structure simple ruthenium (II) polypyridine complex and preparation method thereof. Ruthenium (II) polypyridine complex of the present invention, its complex ion corresponds to the following general formula: The preparation method of ruthenium polypyridine complex of the present invention is carried out as follows:
将Ru(bpy)2Cl2·2H2O与菲罗啉咪唑配体按1∶1摩尔比在水-乙醇(1∶1，v/v)溶剂中回流4-8小时，冷却后过滤，将蒸滤液出去溶剂，加入饱和高氯酸钠水溶液，得沉淀。将此沉淀用柱层析后再加饱和高氯酸钠水溶液沉淀出。经重结晶后得纯净的产物。Ru(bpy)2Cl2·2H2O的制法为：将RuCl3.3H2O与2，2’-联吡啶按摩尔比1∶1于二甲基甲酰胺中回流3小时，浓缩后析出紫黑色结晶，过滤即得。菲罗啉咪唑衍生物配体的合成为：将5，6-菲罗啉二酮与酚醛按1∶1的摩尔比加入2.5当量的醋酸铵在冰醋酸中回流1小时后，冷却，用浓氨水中和，此时析出黄色固体，过滤后用甲醇重结晶得到纯的菲罗啉咪唑衍生物配体，其结构式为：溶剂为乙醇于水的混合溶剂，其体积比为2∶1～5∶1。柱层析可用硅胶或三氧化二铝，淋洗液为丙酮与甲苯的混合物，体积比为2∶1～5∶1。Reflux Ru(bpy) 2 Cl 2 ·2H 2 O and phenanthroline imidazole ligand in a 1:1 molar ratio in water-ethanol (1:1, v/v) solvent for 4-8 hours, filter after cooling, The distilled filtrate was removed from the solvent, and saturated aqueous sodium perchlorate solution was added to obtain a precipitate. The precipitate was precipitated by column chromatography followed by saturated aqueous sodium perchlorate solution. The pure product was obtained after recrystallization. The preparation method of Ru(bpy) 2 Cl 2 ·2H 2 O is: reflux RuCl 3 .3H 2 O and 2,2'-bipyridine in a molar ratio of 1:1 in dimethylformamide for 3 hours, after concentration Precipitated purple black crystals, which can be obtained by filtration. The synthesis of the phenanthroline imidazole derivative ligand is as follows: 5,6-phenanthroline diketone and phenolic aldehyde are added 2.5 equivalents of ammonium acetate at a molar ratio of 1: 1 and refluxed in glacial acetic acid for 1 hour, then cooled and used concentrated Neutralize in ammonia water, at this time, a yellow solid is precipitated, and after filtration, it is recrystallized with methanol to obtain a pure phenanthroline imidazole derivative ligand, and its structural formula is: The solvent is a mixed solvent of ethanol and water, and its volume ratio is 2:1˜5:1. Silica gel or aluminum oxide can be used for column chromatography, and the eluent is a mixture of acetone and toluene, with a volume ratio of 2:1 to 5:1.
本发明制备的钌多吡啶配合物在可见光区有强的吸收，在乙腈和低pH的水溶液中有强的发射，随pH的增加发射减弱，当pH达到烷氧基酚的羟基去质子时，发射强度急剧减弱，表现出高度的pH敏感性，在其pH敏感区内的发射强度变化在50倍左右，可用于高灵敏的发光pH传感器。The ruthenium polypyridine complex prepared by the present invention has strong absorption in the visible light region, and has strong emission in acetonitrile and low pH aqueous solution, and the emission weakens with the increase of pH. When the pH reaches the hydroxyl group of alkoxyphenol to deprotonate, The emission intensity weakens sharply, showing high pH sensitivity, and the emission intensity changes in its pH sensitive region by about 50 times, which can be used as a highly sensitive luminescent pH sensor.
该发明利用酚氧基负离子是强电子给体能有效地淬灭钌(II)多吡啶配合物的发射这一特点，将邻烷氧基酚共价键与钌配合物相连，通过分子内电子转移实现了目标化合物的发射对pH的依赖，利用钌配合物优良的光物理性质及其随pH变化的特性。本发明的配合物的发射对pH的变化十分敏感。在pH5-11范围内，发光强度变化约50倍，可用于高灵敏度的发光pH传感器。The invention utilizes the characteristic that the phenolic anion is a strong electron donor that can effectively quench the emission of the ruthenium (II) polypyridine complex, and connects the o-alkoxyphenol covalently bonded to the ruthenium complex, through intramolecular electron transfer The dependence of the emission of the target compound on pH is realized, and the excellent photophysical properties of the ruthenium complex and its characteristic of changing with pH are utilized. The emission of the complexes of the invention is very sensitive to changes in pH. In the range of pH 5-11, the luminous intensity changes about 50 times, which can be used as a highly sensitive luminescent pH sensor.
下面结合实施例详述本发明Describe the present invention in detail below in conjunction with embodiment
实施例本发明的化合物(结构式如前所述)制备方法如下：0.2mmol Ru(bpy)2Cl2·2H2O，0.2mmol，0.2mmol 4-羟基-3-甲氧基-菲罗啉咪唑配体，20ml乙醇-水(3∶1，v/v)回流5小时，溶液变为棕红色。冷却后过滤，蒸去乙醇加入5ml水溶解后，再加入10ml饱和高氯酸钠水溶液，立即析出黄色沉淀，过滤，用硅胶柱层析，丙酮/甲苯(2∶1，v/v)淋洗得产物。产率75％。此化合物的鉴定紫外吸收：λmax(CH3CN)459.5nm(ε＝2.18×104)。核磁共振：1HNMR(CD3CN)：8.90-8.88(d，2H)，8.57-8.50(t，4H)，8.08-8.07(td，2H)，7.97-7.74(m，8H)，7.65-7.60(m，4H)，7.46-7.42(td，2H)，7.25-7.23(t，2H)，6.83(d，1H)，3.85(s，3H)。元素分析：分子式Ru(C40H30N8)·2ClO4·3H2O，理论值：C，47.72％，H，3.60％，N，11.13％，测量值：C，47.61％，H，3.72％，N，10.91％.yield，73％。上述化合物的pKa值例于表1并有如下的平衡关系：在低pH时，咪唑上的三级N原子质子化，随pH的升高去质子化，发射强度降低。当pH在5~11发射强度急剧下降，其变化大约是50倍，这主要是由于邻甲氧基酚负离子对钌配合物的电子转移淬灭所致。该化合物吸收波长，发射波长，发射量子效率随pH的变化于如表2。表1：配合物的pka值*EXAMPLES The compound of the present invention (structural formula as described above) is prepared as follows: 0.2mmol Ru(bpy) 2 Cl 2 2H 2 O, 0.2mmol, 0.2mmol 4-hydroxy-3-methoxy-phenanthroline imidazole Ligand, 20ml ethanol-water (3:1, v/v) was refluxed for 5 hours, and the solution turned brownish red. After cooling, filter, distill off ethanol and add 5ml of water to dissolve, then add 10ml of saturated sodium perchlorate aqueous solution, immediately precipitate a yellow precipitate, filter, use silica gel column chromatography, rinse with acetone/toluene (2:1, v/v) Get the product. Yield 75%. Identification of this compound UV absorption: λ max (CH 3 CN) 459.5nm (ε=2.18×10 4 ). NMR: 1 HNMR (CD 3 CN): 8.90-8.88 (d, 2H), 8.57-8.50 (t, 4H), 8.08-8.07 (td, 2H), 7.97-7.74 (m, 8H), 7.65-7.60 (m, 4H), 7.46-7.42 (td, 2H), 7.25-7.23 (t, 2H), 6.83 (d, 1H), 3.85 (s, 3H). Elemental analysis: molecular formula Ru(C 40 H 30 N 8 )·2ClO 4 ·3H 2 O, theoretical value: C, 47.72%, H, 3.60%, N, 11.13%, measured value: C, 47.61%, H, 3.72 %, N, 10.91%. yield, 73%. The pKa values of the above-mentioned compounds are shown in Table 1 and have the following equilibrium relationship: At low pH, the tertiary N atom on imidazole is protonated, and deprotonated with increasing pH, and the emission intensity decreases. When the pH is between 5 and 11, the emission intensity drops sharply, and the change is about 50 times, which is mainly due to the electron transfer quenching of the ruthenium complex by the o-methoxyphenoxide anion. The compound absorption wavelength, emission wavelength, and emission quantum efficiency are shown in Table 2 as a function of pH. Table 1: pk a values of complexes*
pka1 pka2 pka3 pka1 * pka2 * pka3 * pk a1 pk a2 pk a3 pk a1 * pk a2 * pk a3 *
1.97 8.5 10.61 / 6.71 /1.97 8.5 10.61 / 6.71 /
pka：通过吸收滴定曲线得到，pka *：通过发射滴定曲线得到。pk a : obtained from an absorption titration curve, pk a * : obtained from an emission titration curve.
所有的测定均在磷酸缓冲溶液中进行，pH范围0.55-12.6.pKa及pKa*通过Henderson-All assays were performed in phosphate buffered solution, pH range 0.55-12.6. pKa and pKa * by Henderson-
Hasselbalch公式：(1).log[(Amax-A)/(A-Amin.)]＝pKa(abs.)-pH，and log[(φmax-φ)/(φ-Hasselbalch formula: (1).log[(A max -A)/(AA min .)]=pKa(abs.)-pH, and log[(φ max -φ)/(φ-
φmin.)]＝pKa(lum.)-pH估算得到.表2.所述化合物在给定pH时的吸收波长、发射波长及发射量子产率φ min .)]=pKa(lum.)-pH is estimated to obtain. Table 2. Absorption wavelength, emission wavelength and emission quantum yield of the compound at a given pH
pH λem max(nm) λabs max(nm) φ×103 pH λ em max (nm) λ abs max (nm) φ×10 3
1 635 436 49.01 635 436 49.0
3 632 458 46.03 632 458 46.0
7 620 460 10.57 620 460 10.5
12 630 462 0.5112 630 462 0.51
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