Rigamonti Luca, Babgi Bandar, Cifuentes Marie P, Roberts Rachel L, Petrie Simon, Stranger Robert, Righetto Stefania, Teshome Ayele, Asselberghs Inge, Clays Koen, Humphrey Mark G
Department of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Inorg Chem. 2009 Apr 20;48(8):3562-72. doi: 10.1021/ic801953z.
The syntheses of trans-[Ru(4,4'-C[triple bond]CC(6)H(4)C[triple bond]CC(6)H(4)NO(2))Cl(dppe)(2)] (19) and the systematically varied complexes trans-[Ru(4,4',4''-C[triple bond]CC(6)H(4)X(2)C(6)H(4)Y(2)C(6)H(4)NO(2))Cl(L(2))(2)] [L(2) = dppe, X(2) = C[triple bond]C, Y(2) = (E)-CH=CH (12), C[triple bond]C (18); L(2) = dppe, X(2) = (E)-CH=CH, Y(2) = C[triple bond]C (14), (E)-CH=CH (16); L(2) = dppm, X(2) = C[triple bond]C, Y(2) = (E)-CH=CH (13); L(2) = dppm, X(2) = (E)-CH=CH, Y(2) = C[triple bond]C (15), (E)-CH=CH (17)] are reported, the latter being donor-bridge-acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. Ru(II/III) oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20,400-23,300 cm(-1) and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon pi-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11,800 cm(-1). Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected beta(0) value on pi-bridge lengthening, a trend that is not seen with beta values because of the blue-shift in lambda(max) for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in beta and beta(0) values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced second-harmonic generation (EFISH) studies at 1907 nm do not afford clear trends.
报道了反式-[Ru(4,4'-C≡CC₆H₄C≡CC₆H₄NO₂)Cl(dppe)₂] (19) 以及系统变化的配合物反式-[Ru(4,4',4''-C≡CC₆H₄X₂C₆H₄Y₂C₆H₄NO₂)Cl(L₂)₂] [L₂ = dppe, X₂ = C≡C, Y₂ = (E)-CH=CH (12), C≡C (18); L₂ = dppe, X₂ = (E)-CH=CH, Y₂ = C≡C (14), (E)-CH=CH (16); L₂ = dppm, X₂ = C≡C, Y₂ = (E)-CH=CH (13); L₂ = dppm, X₂ = (E)-CH=CH, Y₂ = C≡C (15), (E)-CH=CH (17)] 的合成，后者是供体-桥-受体配合物，通过用E-烯键取代炔键改变桥的组成，同时还报道了它们的循环伏安数据、线性光学和二次非线性光学响应数据。在与金属中心相邻的亚苯基处用E-烯键取代炔键，以及用dppm取代dppe作为共配体时，Ru(II/III)氧化电位会升高。低能量光吸收最大值出现在20,400 - 23,300 cm⁻¹区域，其起源是金属到配体的电荷转移(MLCT)；通过添加亚苯基乙炔单元延长π桥以及用炔键取代E-烯键时，这些谱带会发生蓝移。对模型配合物进行的含时密度泛函理论计算给出了低能量谱带的归属。所选氧化态物种的光谱包含以9760 - 11,800 cm⁻¹区域为中心的低能量配体到金属的电荷转移(LMCT)谱带。在1064 nm处通过超瑞利散射(HRS)研究得到的二次分子非线性显示，延长π桥时二级校正的β(0)值会增加，由于这种结构修饰导致λ(max)发生蓝移，所以β值没有呈现出这种趋势。在与金属中心相邻的亚苯基处用E-烯键取代炔键，或用dppe取代dppm共配体，会导致β和β(0)值增加。相比之下，在1300 nm处通过HRS得到的二次分子非线性或在1907 nm处通过电场诱导二次谐波产生(EFISH)研究没有呈现出明显的趋势。
