A conjugated diosma-octacyclic complex and its mixed-valence singly reduced state

作者：Hu, Yu Xuan; Deng, Qianqian; Ou, Ya-Ping; Yang, Xiaofei; Zhang, Jing; Garrett, Emily K.; Zhu, Jun^*; Liu, Sheng Hua^*; Hartl, Frantisek^*

来源：Inorganic Chemistry Frontiers, 2022, 9(22): 5893-5902.

DOI：10.1039/d2qi01523d

• INDEPENDENT CHEMICAL-SHIFTS
• POLYBENZENOID HYDROCARBONS
• DELOCALIZATION
• AROMATICITY
• CHEMISTRY
• METALLABENZENES
• OSMABENZENE
• REACTIVITY
• CRYSTAL
• DENSITY

In this work two dicationic diosma-octacyclic complexes have successfully been synthesized and fully characterized. One of them, with aromatic osmapentalene termini linked by the non-aromatic osmafuran moiety to the rigid naphthalenediolate bridge, represents the first example of a fused, fully conjugated dimetalla-octacyclic complex. A reference complex with more flexible biphenolate in the bridging position was also prepared. Their redox and electronic properties were investigated by combined methods of cyclic voltammetry and UV-vis-NIR-IR spectroelectrochemistry, supported by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The rigid octacyclic complex forms a stable singly reduced mixed-valence species with the spin density localized at one of the osmapentalene termini.

• 单位
  衡阳师范学院; 6; 厦门大学