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A potential long-range electronic coupling between two apical ferrocenyl substituents in the clathrochelate molecule FeDm3(BFc)2 (where Dm2– is dimethylglyoximate dianion) was studied using the electrochemical and the spectroelectrochemical methods with a low ion-pairing ability TBAF {(NBu4 )(B(C6 F5 )4 )} electrolyte. Experimental data are suggestive of a rather poor ability of the quasiaromatic polyazomethine clathrochelate framework to facilitate an intramolecular long-distance electron transfer. Experimental observations were correlated with the theoretical results obtained by Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations.

How Good is Clathrochelate Framework in Facilitating Long-Range Electron-Transfer? Case Study of the Ferrocenylboron-Capped Iron(II) Clathrochelate