Exploring structural complexity in the discovery and self-assembly of a family of nanoscale chalcoxides from {Se 8 Mo 36 } to {Se 26 Mo 68 }.

Herein, we show the controlled generation of multi-component libraries based on the [MoS ₂ O ₂ ] ²⁺ /Mo ^VI O ₄ ^2- /Se ^IV O ₃ ^2- /C ₄ O ₄ ^2- system leading to the formation of a whole new family of nanosized molecular chalcoxides, {Se ₈ Mo ₃₆ } 1, {Se ₈ Mo ₄₀ } 2, {Se ₈ Mo ₅₆ } 3, {Se ₂₀ Mo ₅₆ } 4 and {Se ₂₆ Mo ₆₈ } 5, of the general formula {(MoO ₂ S ₂ ) _a (OH) _b (Se ^IV O ₃ ) _c (C ₄ O ₄ ) _d (MoO ₇ ) _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 Se ^IV O ₃ ^2- and the C ₄ O ₄ ^2- anions lead to the generation of new building blocks, [(MoO ₂ S ₂ ) ₃ (OH) ₆ (C ₄ O ₄ ) (MoO ₇ )] ^4- , and the discovery of a new family of clusters of increasing nuclearity and complexity.