The syntheses of oligo(p-phenylene ethynylene)s (OPEs) end-functionalized by a nitro acceptor group and with a ligated ruthenium unit at varying locations in the OPE chain, namely, trans-[Ru{(C≡C-1,4-C6 H4 )n NO2 }(C≡CR)(dppe)2 ] (dppe=1,2-bis(diphenylphosphino)ethane; n=1, R=1,4-C6 H4 C≡C-1,4-C6 H4 C≡CPh, 1,4-C6 H4 NEt2 ; n=2, R=Ph, 1,4-C6 H4 C≡CPh, 1,4-C6 H4 C≡C-1,4-C6 H4 C≡CPh, 1,4-C6 H4 NO2 , 1,4-C6 H4 NEt2 ; n=3, R=Ph, 1,4-C6 H4 C≡CPh), are reported. Their electrochemical properties were assessed by cyclic voltammetry, their linear optical properties and quadratic and cubic nonlinear optical properties were assayed by UV/Vis/NIR spectroscopy, hyper-Rayleigh scattering studies employing nanosecond pulses at 1064 nm, and broad spectral range Z-scan studies employing femtosecond pulses, respectively, and their linear optical properties and vibrational spectroscopic behavior in the formally RuIII state was examined by UV/Vis/NIR and IR spectroelectrochemistry, respectively. The potentials of the metal-localized oxidation processes are sensitive to alkynyl-ligand modification, but this effect is attenuated on π-bridge lengthening. Computational studies employing time-dependent density functional theory were undertaken on model complexes, with a 2D scan revealing a soft potential-energy surface for intra-alkynyl-ligand aryl-ring rotation; this is consistent with the experimentally observed blueshift in optical absorption maxima. Quadratic optical nonlinearities are significant and cubic NLO coefficients for these small complexes are small. The optimum length of the alkynyl ligands and the ideal metal location in the OPE to maximize the key coefficients have been defined.

中文翻译：

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“刚性杆”双炔基钌络合物的线性光学，二次方和立方非线性光学，电化学和理论研究。

由硝基受体基团末端官能化且在OPE链中不同位置带有连接的钌单元的反式低聚对苯乙炔（OPE）的合成，即反-[Ru {（C≡C-1， 4-C6 H4）n NO2}（C≡CR）（dppe）2]（dppe = 1,2-双（二苯基膦基）乙烷; n = 1，R = 1,4-C6 H4C≡C-1,4 -C6 H4C≡CPh，1,4-C6 H4 NEt2; n = 2，R = Ph，1,4-C6 H4C≡CPh，1,4-C6 H4C≡C-1,4-C6H4 C报告了≡CPh，1，4-C6 H4 NO2、1,4-C6 H4 NEt2； n = 3，R = Ph，1,4-C6 H4C≡CPh）。通过循环伏安法评估了它们的电化学性质，通过紫外/可见/近红外光谱，采用1064 nm纳秒脉冲的超瑞利散射研究以及宽光谱范围Z扫描研究，测定了它们的线性光学性质以及二次和立方非线性光学性质。分别使用飞秒脉冲 分别通过UV / Vis / NIR和IR光谱电化学方法研究了它们在RuIII形式下的线性光学性质和振动光谱行为。金属局部氧化过程的电势对炔基-配体修饰敏感，但这种作用在π桥加长时减弱。在模型配合物上进行了采用时变密度泛函理论的计算研究，并进行了二维扫描，揭示了用于炔基-配体芳基环旋转的软势能表面。这与光学吸收最大值的实验观察到的蓝移一致。二次光学非线性非常重要，这些小分子的三次NLO系数也很小。