Mono(畏5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities

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• 作者：Tiago J. L. Silva ; Paulo J. Mendes ; Ana M. Santos ; M. Helena Garcia ; M. Paula Robalo ; J. P. Prates Ramalho ; A. J. Palace Carvalho ; Marina B眉chert ; Christian Wittenburg ; J眉rgen Heck
• 刊名：Organometallics
• 出版年：2014
• 出版时间：September 22, 2014
• 年：2014
• 卷：33
• 期：18
• 页码：4655-4671
• 全文大小：607K
• ISSN：1520-6041

文摘

A series of mono(畏⁵-cyclopentadienyl)metal(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(畏⁵-C₅H₅)(L)(C鈮{C₄H₂S}_nNO₂)] (M = Fe, L = 魏²-DPPE, n = 1, 2; M = Ru, L= 魏²-DPPE, 2 PPh₃, n = 1, 2; M = Ni, L = PPh₃, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV鈥揤is spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (尾) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push鈥損ull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push鈥損ull systems.