首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Organometallic Complexes for Nonlinear Optics. 24. Reversible Electrochemical Switching of Nonlinear Absorption
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Organometallic Complexes for Nonlinear Optics. 24. Reversible Electrochemical Switching of Nonlinear Absorption

机译:非线性光学的有机金属配合物。 24.非线性吸收的可逆电化学转换

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摘要

The molecular inorganic compounds 1,3,5-{trans-[RuCl(dppe)_2]C≡C-4-C_6H_4C≡C}_3C_6H_3 (1), trans-[Ru(C≡C-4-C_6H_4C≡CPh)Cl(dppe)_2] (2), and trans-[Ru(C≡CPh)Cl(dppm)_2] (3) exhibit reversible oxidation in solution, assigned to the metal-centered Ru~(II/III) processes. Complexes 1-3 are essentially transparent at frequencies below 20 * 10~3 cm~(-1), whereas the green complexes 1~+-3~+ have a strong absorption band centered near 11-12 * 10~3 cm~(-1). These absorption bands have been utilized to demonstrate facile NLO switching utilizing an optically transparent thin-layer electrochemical cell, a procedure which has applicability to evaluating the switching capability of a range of materials. This procedure has been applied to switch cubic nonlinearities, the first electrochromic switching of molecular nonlinear absorption. Oxidation of the molecules results in changes, including changes of sign, of both the imaginary (absorptive) part of the third-order nonlinearity and the real (refractive) part. Cycling between the two forms of the molecules is facile. The sign of the nonlinearity is reversed on oxidation of 1 and 2, whereas 3, a complex with negligible third-order nonlinearity in the resting state, has third-order nonlinearity switched on upon oxidation to 3~+.
机译:分子无机化合物1,3,5- {反式-[RuCl(dppe)_2]C≡C-4-C_6H_4C≡C} _3C_6H_3(1),反式-[Ru(C≡C-4-C_6H_4C≡CPh) Cl(dppe)_2](2)和反-[Ru(C≡CPh)Cl(dppm)_2](3)在溶液中表现出可逆的氧化作用,属于金属中心的Ru〜(II / III)过程。配合物1-3在低于20 * 10〜3 cm〜(-1)的频率下基本上是透明的,而绿色配合物1〜+ -3〜+在11-12 * 10〜3 cm〜(附近)具有较强的吸收带。 -1)。这些吸收带已被用于证明利用光学透明的薄层电化学电池的简便的NLO转换,该方法可用于评估多种材料的转换能力。此过程已应用于切换立方非线性,这是分子非线性吸收的首次电致变色切换。分子的氧化导致三阶非线性的虚部(吸收性)和实部(折光)的变化,包括符号变化。两种形式的分子之间的循环很容易。在1和2的氧化作用下,非线性的符号反转,而在静止状态下具有可忽略的三阶非线性的复合物3在氧化为3〜+时开启了三阶非线性。

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