Exploring structural complexity in the discovery and self-assembly of a family of nanoscale chalcoxides from {Se8Mo36} to {Se26Mo68}

Herein, we show the controlled generation of multi-component libraries based on the [MoV2S2O2]2+/MoVIO42−/SeIVO32−/C4O42− system leading to the formation of a whole new family of nanosized molecular chalcoxides, {Se8Mo36} 1, {Se8Mo40} 2, {Se8Mo56} 3, {Se20Mo56} 4 and {Se26Mo68} 5, of the general formula {(MoV2O2S2)a(OH)b(SeIVO3)c(C4O4)d(MoVI2O7)e}n−, where a, b, c, d, e, n = [16, 20, 8, 6, 2, 20] for 1, [18, 24, 8, 6, 2, 20] for 2, [24, 32, 8, 8, 4, 24] for 3, [28, 32, 20, 8, 0, 32] for 4 and [34, 36, 26, 8, 0, 36] for 5. The coordination modulation effect offered by the SeIVO32− and the C4O42− anions lead to the generation of new building blocks, [(MoV2O2S2)3(OH)6(C4O4) (MoVI2O7)]4−, and the discovery of a new family of clusters of increasing nuclearity and complexity.