Lu Sheng-Jie
College of Chemistry and Chemical Engineering, Heze University, Heze, Shandong Province, 274015, China.
Phys Chem Chem Phys. 2022 Nov 2;24(42):26023-26028. doi: 10.1039/d2cp03977j.
Using anion photoelectron spectroscopy and quantum chemical calculations, the structures and properties of OPt are investigated. The vertical detachment energies (VDEs) of OPt are measured to be 3.28 eV and 3.23 eV through the use of 355 and 266 nm photons, respectively. The high experimental VDEs of OPt can be attributed to the strong Pt-Pt and Pt-O σ bonds and low orbital energy of the SOMO. It is found that neutral OPt has an OPt triangular structure with symmetry and A electronic state. In the neutral OPt, the O atom interacts with the Pt moiety by two 2c-2e PtO bonds, one 3c-2e PtO σ bond, and one 3c-2e PtO π bond. On the other hand, anionic OPt adopts a Pt-Pt-O bent structure with symmetry and A' electronic state. NPA and ELF analyses indicate charge transfer upon complexation from the metal atoms to the O atom. Chemical bonding analyses show that OPt have the strong covalent Pt-Pt and Pt-O bonds, and neutral OPt exhibits σ aromaticity and π antiaromaticity.
利用阴离子光电子能谱和量子化学计算方法，对OPt的结构和性质进行了研究。通过分别使用355和266 nm光子，测得OPt的垂直电子亲合能（VDE）分别为3.28 eV和3.23 eV。OPt较高的实验VDE可归因于强的Pt-Pt和Pt-O σ键以及单占据分子轨道（SOMO）的低轨道能量。研究发现中性OPt具有具有对称性和A电子态的OPt三角形结构。在中性OPt中，O原子通过两个2c-2e PtO键、一个3c-2e PtO σ键和一个3c-2e PtO π键与Pt部分相互作用。另一方面，阴离子OPt采用具有对称性和A'电子态的Pt-Pt-O弯曲结构。自然键轨道（NPA）和扩展拉格朗日键级（ELF）分析表明，络合时发生从金属原子到O原子的电荷转移。化学键分析表明，OPt具有强的共价Pt-Pt和Pt-O键，中性OPt表现出σ芳香性和π反芳香性。
