Electronic Coupling between Two Cyclometalated Ruthenium Centers Bridged by 1,3,6,8-Tetrakis(1-butyl-1H-1,2,3-triazol-4-yl)pyrene
Electronic Coupling between Two Cyclometalated Ruthenium Centers Bridged by 1,3,6,8-Tetrakis(1-butyl-1H-1,2,3-triazol-4-yl)pyrene
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1,3,6,8-四(1-丁基-1H-1,2,3-三唑-4-基)芘桥接的两个环金属化钌中心之间的电子耦合
DOI：
10.1021/ic2005776
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发表时间：
2011-08-01
影响因子：
4.6
通讯作者：
Yao, Jiannian
中科院分区：
文献类型：
--
作者：
Wang, Lei;Yang, Wen-Wen;Yao, Jiannian
设计并合成了一种新型桥联配体1，3，6，8-四（1-丁基-1H-1，2，3-三唑-4-基）芘（ttapyr）。用该配体构建了一个线性双环取代钌（II）配合物[（tpy）Ru（ttapyr）Ru（tpy）]（2+）和一个单环配合物[（tpy）Ru（ttapyr）]（+），其中tpy为2，2 '：6'，2”-三联吡啶。通过电化学方法和光谱方法，借助密度泛函理论计算，对这些配合物的电子性质进行了研究和比较。硝酸铈铵单电子氧化[（tpy）Ru（ttapyr）Ru（tpy）]（3+）生成混合价配合物[（tpy）Ru（ttapyr）Ru（tpy）]（3+）。单个金属中心之间的分子内电子耦合通过价间电荷转移跃迁分析来量化。混价配合物[（tpy）Ru（ttapyr）Ru（tpy）]（3+）在77 K时具有以金属为中心的菱形EPR信号，g因子为2.203。
A new bridging ligand 1,3,6,8-tetralcis(1-butyl-1H-1,2,3-triazol-4-yl)pyrene (ttapyr) was designed and synthesized by "dick" chemistry. This ligand was used to construct a linear dimetallic biscyclometalated Ru(II) complex [(tpy)Ru(ttapyr)Ru(tpy)](2+) and a monometallic complex [(tpy)Ru(ttapyr)](+), where tpy is 2,2':6',2"-terpyridine. The electronic properties of these complexes were studied and compared by electrochemical and spectroscopic methods with the aid of DFT calculations. One-electron oxidation of [(tpy)Ru(ttapyr)Ru(tpy)](3+) with cerium ammonium nitrate produced a mixed-valent complex [(tpy)Ru(ttapyr)Ru(tpy)](3+). The intramolecular electronic coupling between individual metal centers was quantified by the intervalence charge transfer transition analysis. Mixed-valent complex [(tpy)Ru(ttapyr)Ru(tpy)](3+) exhibits a metal-centered rhombic EPR signal at 77 K with an average g factor of 2.203.