Interligand Charge-Transfer Interactions in Electroactive Coordination Frameworks Based on N, N'-Dicyanoquinonediimine (DCNQI).
Inorg Chem
; 57(16): 9766-9774, 2018 Aug 20.
Article
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| MEDLINE
| ID: mdl-29629755
ABSTRACT
Coordination frameworks containing DCNQI2- (DCNQI = N, N'-dicyanoquinonediimine ligand) are produced by deprotonation of DCNQIH2 in the presence of a metal center and a co-ligand. This approach has yielded two-dimensional (2D) sheet compounds [Cd(DCNQI)(L)2] (where L = pyridine (py) or isoquinoline (isoquin)) that can be partially oxidized via solid-state electrochemical and in situ spectroelectrochemical methods to materials that contain DCNQI as its radical monoanion. The new frameworks display charge-transfer bands that are indicative of interligand charge-transfer interactions as supported by TD-DFT computational calculations. The redox-state dependent spectral properties of the frameworks have been probed using a newly developed solid-state spectroelectrochemical cell. Coupled with computational calculations, the experimental data provide an understanding of the fundamental charge-transfer processes that may underpin long-range functional properties such as conductivity in framework materials.
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MEDLINE
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Inorg Chem
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2018
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Article