Extended Dipolar Nonlinear Optical Chromophores Based on trans-Bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) Centers
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- 作者：Benjamin J. Coe ; Josephine L. Harries ; James A. Harris ; Bruce S. Brunschwig ; Peter N. Horton ; Michael B. Hursthouse
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：December 25, 2006
- 年：2006
- 卷：45
- 期：26
- 页码：11019 - 11029
- 全文大小：289K
- 年卷期：v.45,no.26(December 25, 2006)
- ISSN：1520-510X
文摘
Four new complex salts trans-[RuIICl(pdma)2LA][PF6]n [pdma = 1,2-phenylenebis(dimethylarsine); LA = 1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb), n = 1, 1; LA = N-methyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Mebpvb+), n= 2, 2; LA = N-phenyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Phbpvb+), n = 2, 3; LA = N-(2-pyrimidyl)-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Pymbpvb+), n = 2, 4] have been prepared. The electronic absorption spectra of1-4 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with 
max values in the range 432-474nm in acetonitrile. Intense intraligand charge-transfer (ILCT) bands due to LA are also observed, with max valuesin the range 350-416 nm. Cyclic voltammetric studies in acetonitrile reveal reversible RuIII/II waves with E1/2 valuesof ca. 1.05 V vs Ag/AgCl, together with LA-based reduction processes that are irreversible with the exception of 1.Salts 1-4 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K.These studies have afforded dipole moment changes, 
12, for the MLCT and ILCT transitions which have beenused to calculate molecular static first hyperpolarizabilities, 
0, according to the two-state equation 0 = 312(12)2/(Emax)2 (12 = transition dipole moment, Emax = MLCT/ILCT energy). In contrast with related RuII amminecomplexes, replacement of a central E-ethylene bond with a 1,4-phenylene unit does not appear to be an especiallyeffective strategy for combating the NLO transparency-efficiency tradeoff in these pdma complexes. Single-crystalX-ray studies with the complex salts 2 and 3 and also with the pro-ligand salt [Phbpvb+]PF6·0.5HPF6 show thatthese materials all adopt centrosymmetric packing structures.
max values in the range 432-474nm in acetonitrile. Intense intraligand charge-transfer (ILCT) bands due to LA are also observed, with max valuesin the range 350-416 nm. Cyclic voltammetric studies in acetonitrile reveal reversible RuIII/II waves with E1/2 valuesof ca. 1.05 V vs Ag/AgCl, together with LA-based reduction processes that are irreversible with the exception of 1.Salts 1-4 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K.These studies have afforded dipole moment changes, 12, for the MLCT and ILCT transitions which have beenused to calculate molecular static first hyperpolarizabilities, 0, according to the two-state equation 0 = 312(12)2/(Emax)2 (12 = transition dipole moment, Emax = MLCT/ILCT energy). In contrast with related RuII amminecomplexes, replacement of a central E-ethylene bond with a 1,4-phenylene unit does not appear to be an especiallyeffective strategy for combating the NLO transparency-efficiency tradeoff in these pdma complexes. Single-crystalX-ray studies with the complex salts 2 and 3 and also with the pro-ligand salt [Phbpvb+]PF6·0.5HPF6 show thatthese materials all adopt centrosymmetric packing structures.