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Title: Hydricity, electrochemistry, and excited-state chemistry of Ir complexes for CO 2 reduction

Here, we prepared electron-rich derivatives of [Ir(tpy)(ppy)Cl] + with modification of the bidentate (ppy) or tridentate (tpy) ligands in attempt to increase the reactivity for CO 2 reduction and the ability to transfer hydrides (hydricity). Density functional theory (DFT) calculations reveal that complexes with dimethyl-substituted ppy have similar hydricities to the non-substituted parent complex, and photocatalytic CO 2 reduction studies show selective CO formation. Substitution of tpy for bis(benzimidazole)-phenyl or -pyridine (L3 and L4, respectively) induces changes in the physical properties much more pronounced than addition of methyl groups to ppy. Theoretical data predict [Ir(L3)(ppy)(H)] is the strongest hydride donor among complexes studied in this work, but [Ir(L3)(ppy)(NCCH 3)] + cannot be reduced photochemically because the excited state reduction potential is only 0.52 V due to the negative ground state potential of –1.91 V. The excited state [Ir(L4)(ppy)(NCCH 3)] 2+ is the strongest oxidant among complexes studied in this work and the singly reduced species is formed readily upon photolysis in the presence of tertiary amines. Both [Ir(L3)(ppy)(NCCH 3)] + and [Ir(L4)(ppy)(NCCH 3)] 2+ exhibit electrocatalytic current for CO 2 reduction. While a significantly greater overpotential is needed for the L3 complex, a small amount of formate (5-10 %) generationmore » in addition to CO was observed as predicted by the DFT calculations.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Baruch College, CUNY, New York, NY (United States)
Publication Date:
Report Number(s):
BNL-113279-2016-JA
Journal ID: ISSN 1359-6640; FDISE6; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Name: Faraday Discussions; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1337642