1991 Volume 64 Issue 6 Pages 1750-1756
A new bimacrocyclic ligand, in which 13- and 14-membered rings are linked together by a C–C bond, 6-(1,4,7,10-tetraaza-12-cyclotridecyl)-1,4,8,11-tetraazacyclotetradecane (L13−14), and its dinickel(II) complex, [NiII2L13−14]4+, were synthesized. The absorption spectra and cyclic voltammograms of [NiII2L13−14]4+ showed that it has properties of both the 13- and 14-membered rings. Cyclic voltammetry and controlled-potential electrolysis showed that [NiII2L13−14]4+ can serve as an electrocatalyst for water reduction to produce H2. The electrocatalytic efficiency for H2 produclion at −1.5 V was found to be as follows: [NiII2L14−14]4+ (L14−14: 6,6′-bi(1,4,8,11-tetraazacyclotetradecane))>[NiII2L13−14]4+≈[NiIIL14]2+ (L14: 1,4,8,11 -tetraazacyclotetradecane)>>[NiII2L13−13]4+ (L13−13: 12,12′-bi(1,4,7,10-tetraazacyclotridecane)).
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