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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Two-Photon Spectroscopy of a Series of Platinum Acetylides: Conformation-Induced Ground-State Symmetry Breaking
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Two-Photon Spectroscopy of a Series of Platinum Acetylides: Conformation-Induced Ground-State Symmetry Breaking

机译：一系列铂乙酰化铂的两光孔光谱：构象诱导的地面对称性断裂

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摘要

With the goal of elucidating electronic and conformational effects on structure spectroscopic property relationships in platinum acetylides, we synthesized a series of nominally centrosymmetric chromophores trans-Pt(PBu3)(2)(C=C-Phenyl-X)upsilon, where X = diphenylamino (DPA), NH upsilon, OCH3, t-Bu, CH3, H, F, benzothiazole (BTH), CF3, CN, and NO2. We collected one- and two-photon absorption spectra and also performed density functional theory (DFT) and time-dependent (TD) DFT calculations on the ground- and excited-state properties of these compounds. The DFT calculations revealed facile rotation between the two ligands, suggesting that the compounds exhibit nonplanar ground-state conformations in solution. TDDFT calculation of the S-1, state energy and transition dipole moment for a nonplanar conformation gave good agreement with experiment. Two-photon absorption spectra obtained from these compounds allowed estimation of the change of permanent electric dipole moment upon vertical excitation from ground state to S-1 state. The values are small Delta mu < 1.0 D for neutral substituents such as CH3, H, and F but increase sharply to Delta mu approximate to 11 D for electron-accepting NO2. When in a nonplanar conformation, the corresponding calculated Delta mu values showed good agreement with the experimental data indicating that the two-photon spectra result from nonplanar ground-state conformations. Previously studied related chromophores having extended conjugation (Rebane, A.; Drobizhev, M.; Makarov, N. S.; Wicks, G.; Wnuk, P.; Stepanenko, Y.; Haley, J. E.; Krein, D. M.; Fore, J. L.; Burke, A. R.; Slagle, J. E.; McLean, D. G.; Cooper, T. M. J. Phys. Chem. A 2014, 118, 3749-3759) show similar dependence of Delta mu on the substituents, which allows us to conclude that the excited-state properties of these floppy chromophores are a function of the electronic properties of the substituents, ligand size, and nonplanar molecular conformation.
机译：在氨基乙酰乙酯中阐明结构光谱性质关系的目的，我们合成了一系列名义上亚离子发色团Trans-Pt（PBu3）（2）（C = C-Phenyl-X）Upsilon，其中X =二苯基氨基（DPA），NH Upsilon，OCH3，T-BU，CH3，H，F，苯并噻唑（Bth），CF3，CN和No2。我们收集了一个和两光子吸收光谱，并且还对这些化合物的地面和激发状态性质进行了密度函数理论（DFT）和时间依赖性（TD）DFT计算。 DFT计算揭示了两个配体之间的容易旋转，表明化合物在溶液中表现出非平面的地基构象。 TDDFT计算S-1，状态能量和过渡偶极矩的非平面构象与实验吻合良好。从这些化合物获得的双光子吸收光谱允许估计从地态到S-1状态的垂直激发时永久电偶极力矩的变化。该值是用于中性取代基的小δMu<1.0d，例如CH3，H和F，但对于电子接受NO2，近似增加到11天的Δμm。当处于非平面构象时，相应的计算增量MU值与实验数据显示良好的一致性，指示双光子谱由非平面地位构象结果产生。以前研究过的相关发色团，具有扩展共轭（rebane，a .; drobizhev，m .; makarov，ns;灯芯，g .; wnuk，p .; stepanenko，y .; haley，je; kerin，dm; feed，jl; burke ，ar; sl sl，JE;麦克莱恩，DG; Cooper，TMJ Phys。Chem。Chem。2014,118,3749-3759）显示了δme在取代基的类似依赖性，这使我们能够得出以下兴奋状态性质软体发色团是取代基，配体尺寸和非平面分子构象的电子性质的函数。

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