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

Abstract

Herein, we show the controlled generation of multi-component libraries based on the [Mo^V₂S₂O₂]²⁺/Mo^VIO₄²⁻/Se^IVO₃²⁻/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 {(Mo^V₂O₂S₂)_a(OH)_b(Se^IVO₃)_c(C₄O₄)_d(Mo^VI₂O₇)_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^IVO₃²⁻ and the C₄O₄²⁻ anions lead to the generation of new building blocks, [(Mo^V₂O₂S₂)₃(OH)₆(C₄O₄) (Mo^VI₂O₇)]⁴⁻, and the discovery of a new family of clusters of increasing nuclearity and complexity.