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首页> 外文期刊>Chemistry: A European journal >Influence of Central Metalloligand Geometry on Electronic Communication between Metals: Syntheses, Crystal Structures, MMCT Properties of Isomeric Cyanido-Bridged Fe_2Ru Complexes, and TDDFT Calculations
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Influence of Central Metalloligand Geometry on Electronic Communication between Metals: Syntheses, Crystal Structures, MMCT Properties of Isomeric Cyanido-Bridged Fe_2Ru Complexes, and TDDFT Calculations

机译：中心金属配体的几何形状对金属之间电子通信的影响：合成，晶体结构，异氰酸酯桥联的Fe_2Ru配合物的MMCT特性和TDDFT计算

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摘要

To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal chargetransfer (MMCT) properties of polynuclear complexes, cisand trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans- [Cp(dppe)Fe~(II)NCRu~(II)(phen)_2CN-Fe~(II)(dppe)Cp][PF_6]_2 (cis/trans- 1[PF_6]_2), cis/trans-[Cp(dppe)Fe~(II)NCRu~(II)(phen)2CNFe~(III)-(dppe)- Cp][PF_6]_3 (cis/trans-1[PF_6]_3) and cis/trans-[Cp(dppe)Fe~(III)NCRu~(II)- (phen)_2CN-Fe~(III)(dppe)Cp][PF_6]_4 (cis/trans-1[PF_6]_4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe~(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF_6]_2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF_6]_3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru~(II)-CN-Fe~(II) subunit to a Fe~(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF_6]_3 is lower than that in cis-1[PF_6]_3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF_6]_4 possesses lower vicinal Ru~(II)→Fe~(III) MMCT transition energy than cis-1[PF_6]_4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations.
机译：研究中心金属配体的几何形状如何影响多核配合物，顺式和反式异构异三金属配合物及其一电子和二电子氧化产物顺式/反式[Cp（ dppe）Fe〜（II）NCRu〜（II）（phen）_2CN-Fe〜（II）（dppe）Cp] [PF_6] _2（cis / trans-1 [PF_6] _2），cis / trans- [Cp（ dppe）Fe〜（II）NCRu〜（II）（phen）2CNFe〜（III）-（dppe）-Cp] [PF_6] _3（cis / trans-1 [PF_6] _3）和cis / trans- [Cp（合成并表征了dppe）Fe〜（III）NCRu〜（II）-（phen）_2CN-Fe〜（III）（dppe）Cp] [PF_6] _4（cis / trans-1 [PF_6] _4）。电化学测量表明，在顺式和反式异构体顺式/反式-1 [PF_6] _2的两个外部Fe〜（II）原子之间存在电子相互作用。研究了所有这些配合物的电子性质，并通过光谱技术和TDDFT // DFT计算进行了比较。不出所料，这两种混合价复合物cis / trans-1 [PF_6] _3在NIR区域均显示出不同的强吸收信号，这主要应归因于从Ru〜（II）-CN-上离域的MO的跃迁。 Fe〜（II）亚基为Fe〜（III）d轨道，并有一些共配体。此外，trans-1 [PF_6] _3的NIR跃迁能量低于cis-1 [PF_6] _3的NIR跃迁能量，这与基于分子轨道分析的分子轨道的对称性有关。另外，双电子氧化配合物的电子光谱表明，反式-1 [PF_6] _4具有比顺式[1] [PF_6] _4更低的邻位Ru〜（II）→Fe〜（III）MMCT跃迁能。此外，使用TDDFT // DFT计算可以很好地合理化氧化产物的MMCT跃迁的分配以及顺式和反式复合物之间电子性质的差异。

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