Hydrogen-Bonded Extended Arrays of the [Re63-Se)8]2+ Core-Containing Clusters

Site-differentiated solvated clusters of the general formula [Re63-Se)8(PEt3)n(MeCN)6-n](SbF6)2 (n = 4, cis and trans; n = 5) undergo ligand substitution reaction with isonicotinamide to afford the corresponding amide derivatives, [Re63-Se)8(PEt3)n(isonicotinamide)6-n]2+ [1 (n = 5); 2 (n = 4, trans); 3 (n = 4, cis)]. Retention of stereochemistry in each case was confirmed by 1H and 31P NMR. The solid-state structures of all three compounds were established crystallographically, which revealed self-complementary hydrogen-bonding interactions between adjacent cluster units. While complex 1 exists as hydrogen-bonded dimers in the solid state, compounds 2 and 3 form one-dimensional chains of clusters bridged by paired hydrogen bonds. It is the rigid stereochemistry of the cluster, combined with the classic crystal engineering motif of complementary N−H···O amide hydrogen bonding, that affords the predictable solid-state structures and dimensionality.