A conjugated diosma-octacyclic complex and its mixed-valence singly reduced state. Issue 22 (4th October 2022)

• Record Type: Journal Article
• Authors: Hu, Yu Xuan; Deng, Qianqian; Ou, Ya-Ping; Yang, Xiaofei; Zhang, Jing; Garrett, Emily K.; Zhu, Jun; Liu, Sheng Hua; Hartl, František
• Is Part Of: Inorganic chemistry frontiers. Volume 9:Issue 22(2022)
• Page Start: 5893
• Page End: 5902
• Publication Date: 2022-10-04
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2qi01523d
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : A conjugated diosma-octacyclic complex, with aromatic osmapentalene termini and the rigid naphthalene bridge linked by non-aromatic osmafuran rings, forms a singly reduced valence-trapped species characterised at low temperature. Abstract : 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.