Mixed valency in a neutral 1D Fe-chloranilate coordination polymer

Katelyn M Clutterbuck; Brendan F Abrahams; Timothy A Hudson; Martin P van Koeverden

doi:10.1039/d1dt04368d

Mixed valency in a neutral 1D Fe-chloranilate coordination polymer

Dalton Trans. 2022 Jun 21;51(24):9199-9205. doi: 10.1039/d1dt04368d.

Authors

Katelyn M Clutterbuck¹, Brendan F Abrahams¹, Timothy A Hudson¹, Martin P van Koeverden¹

Affiliation

¹ School of Chemistry, University of Melbourne, Parkville, Victoria 3010, Australia. bfa@unimelb.edu.au.

PMID: 35671447
DOI: 10.1039/d1dt04368d

Abstract

The syntheses and structures of a pair of neutral one-dimensional (1D) Fe-anilate based coordination polymers, Fe(Fan)(4,4'-bipy)₂ (Fan^n- = deprotonated 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone; 4,4'-bipy = 4,4'-bipyridine) and Fe(Clan)(OPPh₃)₂ (Clan^n- = deprotonated 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone; OPPh₃ = triphenylphosphine oxide), are reported. In the case of Fe(Fan)(4,4'-bipy)₂, the Fe centre is in the +2 oxidation state and the Fan ligand is present in its quinoidal, dianionic form. In contrast, the structurally similar Fe(Clan)(OPPh₃)₂ chain contains Fe centres and chloranilate ligands in oxidation states close to +3 and -3 respectively at low temperature. It is suggested that intrachain π-π interactions aid electron transfer from the Fe centres to the bridging ligands.