Supramolecular Networks Extended by N–H···O Interactions between Cu‐Benzimidazole Subunits and Keggin Anions

Three new 2D/3D supramolecular architectures derived from Cu‐organic subunits and Keggin anions, [Cu II 2 (biz) 8 (HPMo VI 10 Mo V 2 O 40 )(H 2 O) 2 ] · 2H 2 O ( 1 ), [Cu I 4 (biz) 8 (SiW 12 O 40 )] · 2H 2 O ( 2 ) and [Cu I 2 (dmbiz) 4 (Hdmbiz) 2 (SiW 12 O 40 )] ( 3 ) (biz = benzimidazole, dmbiz = 5, 6‐dimethyl benzimidazole), were obtained under hydrothermal conditions. Single crystal X‐ray diffraction analysis reveals that compound 1 has two kinds of [Cu II (biz) 2 ] 2+ cations, which are further extended by Keggin anions into a 2D (4, 8)‐connected supramolecular network by hydrogen bonding interactions. In compound 2 , four types of [Cu I (biz) 2 ] + subunits link the [SiW 12 O 40 ] 4– anions to form a 3D (2, 6)‐connected supramolecular structure. Compound 3 shows a 3D supramolecular network with a NaCl‐type topology constructed by [Cu I (dmbiz) 2 ] + subunits, anions, and discrete [Hdmbiz] + cations. Moreover, the electrochemical and photocatalytic properties of compounds 1 and 2 were investigated.