Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges
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- 作者：Huihua Zhang ; Dr. Mahbod Morshedi ; Mahesh S. Kodikara ; Dr. Graeme J. Moxey ; Dr. Genmiao Wang ; Huan Wang ; Cristó ; bal Quintana ; Em. Prof. Rob Stranger ; Prof. Chi Zhang ; Prof. Marie P. Cifuentes and Prof. Mark G. Humphrey
- 刊名：ChemPlusChem
- 出版年：2016
- 出版时间：July 2016
- 年：2016
- 卷：81
- 期：7
- 页码：613-620
- 全文大小：643K
- ISSN：2192-6506
文摘
The syntheses of oligo(p-phenylenevinylene)s (OPVs) end-functionalized with a ligated ruthenium alkynyl unit as a donor and a nitro as acceptor, namely trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru4), trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru6), and trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru8), are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), their linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis-NIR spectroscopy and hyper-Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally RuIII state examined by UV/Vis-NIR spectroelectrochemistry. Computational studies employing time-dependent density functional theory were undertaken on model complexes to rationalize the optical observations.