含氮、氧新配体及配合物的合成、结构和应用
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摘要
含有两或三个吡啶环的吡啶配体的钌配合物，因为具有化学性质稳定、结构容易修饰、光学性质丰富等特点，其与核酸的相互作用，成为人们的研究热点，可以发展出核酸结构的光谱探针和治癌药物。多吡啶等配体的多核锰配合物在光系统Ⅱ放氧中心的结构和／或功能模拟方面发挥了重要的作用，可用于分解水催化剂的研究开发。因此，本文作了以下的研究工作：
本文以邻菲咯啉为原料，邻菲咯啉-5，6-二酮为中间体，分别与3-醛基吡唑和2-醛基咪唑反应，合成了两个未见文献报道的含咪唑多吡啶配体2-(3-咪唑基)咪唑并[4，5-f]邻菲咯啉(IZIP)和2-(3-吡唑基)咪唑并[4，5-f]邻菲咯啉(PZIP)。以这两个配体合成了两个钌配合物[(bpy)_2Ru(IZIP)](ClO_4)_2(Rul)及[(bpy)_2Ru(PZIP)](ClO_4)_2(Ru_2)(其中bpy为2，2’-联吡啶)。用邻菲咯啉-5，6-二酮和二乙烯三胺反应合成了(1R)-6，9，15，18，21-pentaazapentacyclo[12.7.0.0~(1,18).0~(2,7).0~(8,13)]henicosa-2，4，6，8(13)，9，11，14-heptaene。用3，4-二羟基苯甲醛为原料，在MnCl_2存在条件下合成了(5R，10R)-3，8-dihydroxy-5，10-diethoxy-5，10-dihydrochromeno[5，4，3-cde]chromene monohydrate，得到其两个超分子异构体。通过质谱，核磁共振氢谱，电子吸收光谱，发光光谱，红外光谱，X-射线单晶衍射等手段对这些化合物进行了结构表征和性质研究。
通过电子吸收光谱、稳态发光光谱、稳态发光猝灭、粘度测量等光物理性质测量方法，研究了Ru1和Ru2与小牛胸腺DNA的作用情况。发现两者与DNA都发生了明显的结合，表现在与DNA结合前后配合物光谱性质的明显改变。DNA的加入使两者的紫外和可见吸收峰都出现了减色现象。加入DNA后，配合物溶液在600nm附近的发光明显增强。而且结合DNA后发光受猝灭剂猝灭的可能性显著降低。DNA的相对粘度在加入配合物后，出现了增大的现象，其中Ru1的增大幅度要比Ru2的大。由于bpy小的平面性使得它不具有插入DNA的功能，因此说明两个配合物分别以配体IZIP及PZIP插入的方式与DNA作用的。
本文还现场合成了以4-甲基苯基-2，2’：6’，2”-三吡啶及其两种衍生物4-溴甲基苯基-2，2’：6’，2”-三吡啶、4-醛基苯基-2，2’：6’，2”-三吡啶作为配体(L)的双核锰配合物[L_2(H_2O)_2Mn_2(μ-O)_2](NO_3)_3，并对它们进行了催化氧化水分解放氧性质的测试研究。结果表明三种双核锰配合物在氧化剂过硫酸氢钾的作用下，都具有氧化水放氧的性能，但是可能由于修饰基团与锰原子的距离较远，对锰原子的影响较小，所以三者的放氧速率差别不大。
The ruthenium complexes of ligands containing 2 or 3 pyridine rings have goodproperties in chemical stability, easy tuning in structure and rich photophysicalbehavior. Their interaction with nucleic acids has been the subject of tremendousresearch interest and has potential to develop spectroscopic probes of DNA structureand cancer therapy agents. Multinuclear manganese complexes of polypyridineligands have played an important role in mimicking the oxygen-evolving center ofphotosystemⅡstructurally and/or functionally and are applicable in developing watersplitting catalysts. This thesis has described original research work as follows:The reaction between 1,10-phenanthroline-5,6-dione and pyrazole-3-carbaldehydeor imidazole-2-carbaldehyde has generated two new ligands2-(1H-imidazol-2-yl)- 1H-imidazo[4,5-f] [1,10]phenanthroline (IZIP) and2-(1H-pyrazol-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (PZIP), respectively.The corresponding ruthemium complexes [(bpy)_2Ru(IZIP)](ClO_4)_2 (denoted as Ru1)and [(bpy)_2Ru(PZIP)](ClO_4)_2 (Ru2) (bpy is 2,2'-bipyridine) have then beensynthesized. Two novel polycyclic compounds rich in N and O atoms have beensynthesized through reactions of 1,10-phenanthroline-5,6-dione withdiethylenetriamine, or reactions of 3,4-dihydroxybenzaldehyde in the presence ofmanganese chloride, respectively. They are (1R)-6,9,15,18,21-pentaazapentacyclo[12.7.0.0~(1,18).0~(2,7).0~(8,13)]henicosa-2,4,6,8(13),9,11,14-heptaene and(5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromenemonohydrate, respectively. For the latter, two supramolecular isomers have beenobtained. Means of ESI-MS, ~1H NMR, electronic absorption, emission, IRand single crystal X-ray diffraction have been utilized for characterizing and property studies of these compounds.
Photophysical methods including electronic absorption, emission and emissionquenching, and viscosity measurement have been used to study the interaction of Ru1,Ru2 with calf thymus DNA. Both complexes bind significantly to DNA, as shown bythe significant differences between the photophysical properties before and afterbinding with DNA. Addition of DNA to Ru1 and Ru2 led to hypochromism in bothultraviolet and visible regions and enhancement of the emission of the two complexes.The emission quenching by K_4[Fe(CN)_6] was decreased greatly when DNA waspresent. The relative viscosity of DNA was raised after adding these two complexes tosaturation with the order Ru1＞Ru2. Since the small planarity of bpy makes it a poormoiety for intercalating DNA, the above facts imply that Ru1 and Ru2 bind to DNAby intercalation of IZIP or PZIP into the DNA base pairs.
Three dinuclear manganese complexes [L_2(H_2O)_2Mn_2(μ-O)_2](NO_3)_3, in which Lis 4-tolyl-2,2':6',2"-terpyridine, 4-bromomethylphenyl-2,2':6',2"-terpyridine,4-formylphenyl-2,2':6',2"-terpyridine have been prepared in situ, and their activity ofcatalyzing the oxidation of water to molecular oxygen. The results show that all ofthem can catalyze O_2 evolution reaction with oxidant oxone, but probably because theterminal substituents are far away from and have unconspicuous effect on Mn atoms,the rates of O_2 evolution of the three complexes are close.
本文以邻菲咯啉为原料，邻菲咯啉-5，6-二酮为中间体，分别与3-醛基吡唑和2-醛基咪唑反应，合成了两个未见文献报道的含咪唑多吡啶配体2-(3-咪唑基)咪唑并[4，5-f]邻菲咯啉(IZIP)和2-(3-吡唑基)咪唑并[4，5-f]邻菲咯啉(PZIP)。以这两个配体合成了两个钌配合物[(bpy)_2Ru(IZIP)](ClO_4)_2(Rul)及[(bpy)_2Ru(PZIP)](ClO_4)_2(Ru_2)(其中bpy为2，2’-联吡啶)。用邻菲咯啉-5，6-二酮和二乙烯三胺反应合成了(1R)-6，9，15，18，21-pentaazapentacyclo[12.7.0.0~(1,18).0~(2,7).0~(8,13)]henicosa-2，4，6，8(13)，9，11，14-heptaene。用3，4-二羟基苯甲醛为原料，在MnCl_2存在条件下合成了(5R，10R)-3，8-dihydroxy-5，10-diethoxy-5，10-dihydrochromeno[5，4，3-cde]chromene monohydrate，得到其两个超分子异构体。通过质谱，核磁共振氢谱，电子吸收光谱，发光光谱，红外光谱，X-射线单晶衍射等手段对这些化合物进行了结构表征和性质研究。
通过电子吸收光谱、稳态发光光谱、稳态发光猝灭、粘度测量等光物理性质测量方法，研究了Ru1和Ru2与小牛胸腺DNA的作用情况。发现两者与DNA都发生了明显的结合，表现在与DNA结合前后配合物光谱性质的明显改变。DNA的加入使两者的紫外和可见吸收峰都出现了减色现象。加入DNA后，配合物溶液在600nm附近的发光明显增强。而且结合DNA后发光受猝灭剂猝灭的可能性显著降低。DNA的相对粘度在加入配合物后，出现了增大的现象，其中Ru1的增大幅度要比Ru2的大。由于bpy小的平面性使得它不具有插入DNA的功能，因此说明两个配合物分别以配体IZIP及PZIP插入的方式与DNA作用的。
本文还现场合成了以4-甲基苯基-2，2’：6’，2”-三吡啶及其两种衍生物4-溴甲基苯基-2，2’：6’，2”-三吡啶、4-醛基苯基-2，2’：6’，2”-三吡啶作为配体(L)的双核锰配合物[L_2(H_2O)_2Mn_2(μ-O)_2](NO_3)_3，并对它们进行了催化氧化水分解放氧性质的测试研究。结果表明三种双核锰配合物在氧化剂过硫酸氢钾的作用下，都具有氧化水放氧的性能，但是可能由于修饰基团与锰原子的距离较远，对锰原子的影响较小，所以三者的放氧速率差别不大。
The ruthenium complexes of ligands containing 2 or 3 pyridine rings have goodproperties in chemical stability, easy tuning in structure and rich photophysicalbehavior. Their interaction with nucleic acids has been the subject of tremendousresearch interest and has potential to develop spectroscopic probes of DNA structureand cancer therapy agents. Multinuclear manganese complexes of polypyridineligands have played an important role in mimicking the oxygen-evolving center ofphotosystemⅡstructurally and/or functionally and are applicable in developing watersplitting catalysts. This thesis has described original research work as follows:The reaction between 1,10-phenanthroline-5,6-dione and pyrazole-3-carbaldehydeor imidazole-2-carbaldehyde has generated two new ligands2-(1H-imidazol-2-yl)- 1H-imidazo[4,5-f] [1,10]phenanthroline (IZIP) and2-(1H-pyrazol-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (PZIP), respectively.The corresponding ruthemium complexes [(bpy)_2Ru(IZIP)](ClO_4)_2 (denoted as Ru1)and [(bpy)_2Ru(PZIP)](ClO_4)_2 (Ru2) (bpy is 2,2'-bipyridine) have then beensynthesized. Two novel polycyclic compounds rich in N and O atoms have beensynthesized through reactions of 1,10-phenanthroline-5,6-dione withdiethylenetriamine, or reactions of 3,4-dihydroxybenzaldehyde in the presence ofmanganese chloride, respectively. They are (1R)-6,9,15,18,21-pentaazapentacyclo[12.7.0.0~(1,18).0~(2,7).0~(8,13)]henicosa-2,4,6,8(13),9,11,14-heptaene and(5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromenemonohydrate, respectively. For the latter, two supramolecular isomers have beenobtained. Means of ESI-MS, ~1H NMR, electronic absorption, emission, IRand single crystal X-ray diffraction have been utilized for characterizing and property studies of these compounds.
Photophysical methods including electronic absorption, emission and emissionquenching, and viscosity measurement have been used to study the interaction of Ru1,Ru2 with calf thymus DNA. Both complexes bind significantly to DNA, as shown bythe significant differences between the photophysical properties before and afterbinding with DNA. Addition of DNA to Ru1 and Ru2 led to hypochromism in bothultraviolet and visible regions and enhancement of the emission of the two complexes.The emission quenching by K_4[Fe(CN)_6] was decreased greatly when DNA waspresent. The relative viscosity of DNA was raised after adding these two complexes tosaturation with the order Ru1＞Ru2. Since the small planarity of bpy makes it a poormoiety for intercalating DNA, the above facts imply that Ru1 and Ru2 bind to DNAby intercalation of IZIP or PZIP into the DNA base pairs.
Three dinuclear manganese complexes [L_2(H_2O)_2Mn_2(μ-O)_2](NO_3)_3, in which Lis 4-tolyl-2,2':6',2"-terpyridine, 4-bromomethylphenyl-2,2':6',2"-terpyridine,4-formylphenyl-2,2':6',2"-terpyridine have been prepared in situ, and their activity ofcatalyzing the oxidation of water to molecular oxygen. The results show that all ofthem can catalyze O_2 evolution reaction with oxidant oxone, but probably because theterminal substituents are far away from and have unconspicuous effect on Mn atoms,the rates of O_2 evolution of the three complexes are close.
引文
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