We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Electronic Structures of Divinylchalcogenophene-Bridged Biruthenium Complexes: Exploring Trends from O to Te.
- Authors
Liu, Wen‐Xia; Yan, Feng; Qian, Shu‐Li; Ye, Jin‐Yu; Liu, Xu; Yu, Ming‐Xia; Wu, Xiao‐Hui; Le, Meng‐Lei; Zhou, Zhi‐You; Liu, Sheng‐Hua; Low, Paul J.; Jin, Shan
- Abstract
An homologous series of divinylchalcogenophene-bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2-(μ-CH=CH-C4H2E-CH=CH)] (4a-4d, E = O, S, Se, Te) have been synthesised and fully characterised by X-ray crystallography and various spectroscopic techniques. The single-crystal X-ray diffraction results reveal a distinct short/long bond-length alternation along the polyene-like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu-Ru) in complexes 4a-4d as the heteroatom in the five-membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one-electron oxidation processes, the half-wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re-organisation energies. Analysis of [4a-4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectro-electrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene-like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a-4d]+, the charge is rather effectively delocalised over the 10-atom Ru--[4-s-cis-all-trans-(CH=CH)4]--Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.
- Subjects
RUTHENIUM compounds; ELECTRONIC structure; METAL complexes; X-ray crystallography; HYDROCARBONS; VINYL polymers
- Publication
European Journal of Inorganic Chemistry, 2017, Vol 2017, Issue 43, p5015
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201701036