Variable electronic structure and spin distribution in bis(2,2′-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- And 4,5-diimido-pyrene

0541660 - ÚFCH JH 2022 RIV GB eng J - Journal Article
Chatterjee, M. - Mondal, S. - Hazari, A. S. - Záliš, Stanislav - Kaim, W. - Lahiri, G. K.
Variable electronic structure and spin distribution in bis(2,2′-bipyridine)-metal complexes (M = Ru or Os) of 4,5-dioxido- And 4,5-diimido-pyrene.
Dalton Transactions. Roč. 50, č. 12 (2021), s. 4191-4201. ISSN 1477-9226. E-ISSN 1477-9234
Grant - others:Ga MŠk(CZ) LM2015070
Institutional support: RVO:61388955
Keywords : bis(2,2′-bipyridine)-metal complexes (M = Ru or Os) * 4,5-dioxido- And 4,5-diimido-pyrene * TD-DFT
OECD category: Physical chemistry
Impact factor: 4.569, year: 2021
Method of publishing: Limited access

he odd-electron compounds [M(bpy)2(L1)](ClO4) M = Ru ([1](ClO4)) or Os ([2](ClO4)), and the even-electron species [M(bpy)2(H2L2)](ClO4)2, M = Ru ([3](ClO4)2) or Os ([4](ClO4)2) were obtained from pyrene-4,5-dione, L1, or 4,5-diaminopyrene, H4L2, and were characterised structurally, electrochemically and spectroscopically. Experimental and computational analysis (TD-DFT) revealed rather different electronic structures and spin distributions of the paramagnetic monocations1+-4+. EPR investigations and electronic absorption studies exhibit increasing metal contributions to the singly occupied MO along the series1+<3+<4+<2+, illustrated bygvalue and long-wavelength absorbance. In addition to variations of the metal (Ru,Os) and the donor atoms (O,NH) the extension of the π system of the semiquinone-type ligand has a large effect on the electronic structure of the paramagnetic cations.
Permanent Link: http://hdl.handle.net/11104/0319192