Tuning PtII‐Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis
Tuning PtII‐Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis
复制标题
通过配体设计调节基于 PtII 的供体-受体系统：对前沿轨道、氧化还原电位、紫外/可见/近红外吸收、电致变色和光催化的影响
作者：
S. Sobottka;Maite Nößler;Andrew L. Ostericher;G. Hermann;Noah Subat;Julia Beerhues;Margarethe Behr;Lisa Suntrup;Uta Albold;S. Hohloch;J. Tremblay;B. Sarkar
摘要 本文提出了不对称铂供体-受体配合物 [(pimp)Pt(Q2−)]，其中 pimp=[(2,4,6-三甲基苯基亚氨基)甲基]吡啶和 Q2−=儿茶酚型供体配体。配合物的性质根据供体配体的函数进行评估，并绘制电化学、光学和理论数据之间的相关性。特别关注以磺酰基取代的苯二酰胺配体为特征的配合物的光谱电化学研究，该配体在氧化时表现出氧化还原诱导的键异构现象。时间相关密度泛函理论（TD-DFT）以及电子通量密度分析已被用来合理化配合物的光谱及其反应性。化合物1（[(pimp)Pt(Q2−)]，其中Q2−=3,5-二叔丁基儿茶酚酸酯）被证明是一种有效的分子氧光敏剂，随后被用于光化学交叉脱氢偶联（CDC）反应。因此，这些结果展示了供体-受体系统的新途径，包括它们作为有机转化光催化剂的作用，以及通过在供体配体上使用磺酰胺取代基在这些化合物中引入氧化还原诱导的键异构现象的可能性。
Abstract Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6‐trimethylphenylimino)methyl]pyridine and Q2−=catecholate‐type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl‐substituted phenylendiamide ligands, which show redox‐induced linkage isomerism upon oxidation. Time‐dependent density functional theory (TD‐DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5‐di‐tert‐butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross‐dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox‐induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.
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