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Main-chain organometallic polymers comprising redox-active iron(II) centers connected by ditopic N-heterocyclic carbenes
Mercs, Laszlo; Neels, Antonia; Stoeckli-Evans, Helen; Albrecht, Martin
Main-chain organometallic polymers were synthesized from bimetallic iron(II)complexes containing a ditopic N-heterocyclic carbene (NHC) ligand [(cp)(CO)LFe(NHC~NHC)Fe (cp)(CO)L]X2 (where NHC~NHC represents a bridging dicarbene ligand, L = Iā€“ or CO). Addition of a diimine ligand such as pyrazine or 4,4ā€™-bipyridine interconnected these bimetallic complexes and gave the corresponding co-polymers containing iron centers that are alternately linked by a dicarbene and a diimine ligand. Diimine coordination was depending on the wingtip groups at the carbene ligands and was accomplished either by photolytic activation of a carbonyl ligand from the cationic [Fe(cp)(NHC)(CO)2]+ precursor (alkyl wingtips) or by AgBF4-mediated halide abstraction from the neutral complex [FeI(cp)(NHC)(CO)] (mesityl wingtips). Remarkably, the polymeric materials were substantially more stable than the related bimetallic model complexes. Electrochemical analyses indicated metal-metal interactions in the pyrazine-containing polymers, whereas in 4,4ā€™-bipyridine-linked systems the metal centers were electronically decoupled. Other funder Swiss National Science Foundation Alfred Werner Foundation sp, ke, ab, jo, is - TS 15.05.12
Keyword(s): Iron; N-heterocyclic carbene; Main chain polymer; Electrochemistry; Carbenes (Methylene compounds); Organometallic polymers; Electrochemical analysis
Publication Date:
2012
Type: Journal article
Peer-Reviewed: Unknown
Language(s): English
Institution: University College Dublin
Publisher(s): RSC
File Format(s): other; application/pdf
First Indexed: 2012-08-25 05:15:26 Last Updated: 2018-10-11 15:53:50