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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic Spectra of the Cyclometalated Complexes M(2-thienylpyridine)_2 with M = Pd, Pt: A Theoretical Study
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Electronic Spectra of the Cyclometalated Complexes M(2-thienylpyridine)_2 with M = Pd, Pt: A Theoretical Study

机译：环金属化配合物M（2-噻吩基吡啶）_2的电子光谱，M = Pd，Pt：理论研究

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摘要

The optical spectra of the cyclometalated complexes Pd, Pt(thpy)_2, with thpy~-, the deprotonated form of 2-(2-thienyl)pyridine, have been calculated using a multiconfigurational second-order perturbation treatment based on a complete active space reference wave function, i.e., the CASSCF/CASPT2 method. The calculations were performed on optimized structures within C_(2v) symmetry, obtained using density functional theory (DFT). The structure and lowest excited states of free protonated thpyH were also calculated. On the basis of the calculated results for excitation energies and oscillator strengths, the most important bands in the experimental absorption spectra of the complexes were assigned as excitations to states of symmetry ~1A_1 or ~1B_2, all of mixed charge-transfer/ligand-centered character. The lowest triplet excited state was calculated to be the a ~3A_1 state, closely followed by the ~3B_2 state. Both excitations were found to be almost purely ligand-centered, with a very limited charge-transfer contribution in Pd(thpy)_2 and an only slightly larger contribution in Pt(thpy)_2. The differences between the position and character of the singlet excited states in the absorption spectra of both molecules are also discussed. The results are found to be consistent with the trends obtained from previous experimental measurements.
机译：环金属化配合物Pd，Pt（thpy）_2与thpy〜-（2-（2-噻吩基）吡啶的去质子化形式）的光谱已基于完整的活性空间使用多构型二阶扰动处理进行了计算参考波函数，即CASSCF / CASPT2方法。对使用密度泛函理论（DFT）获得的C_（2v）对称性内的优化结构进行了计算。还计算了游离质子化的thpyH的结构和最低激发态。根据激发能和振子强度的计算结果，将配合物实验吸收光谱中最重要的谱带作为激发，分配给对称状态〜1A_1或〜1B_2，所有混合电荷转移/配体中心字符。计算出最低的三重态激发态为〜3A_1状态，紧随其后的是〜3B_2状态。发现这两种激发几乎都是纯粹以配体为中心的，在Pd（thpy）_2中的电荷转移贡献非常有限，而在Pt（thpy）_2中的贡献稍大。还讨论了两个分子的吸收光谱中单线态激发态的位置和特征之间的差异。发现结果与从先前实验测量获得的趋势一致。

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