Tunable bandgaps in self-assembled transition metal-incorporated heterometallic MSb (M = V, Mn, Co, Ni, and Cu) oxo clusters.

This paper investigates the reactivity and optical properties of transition metal-incorporated organoantimony(V) clusters prepared by a solvothermal route. The detailed structural characterization of novel heterometallic MSb oxo clusters is reported herein. Single crystal X-ray diffraction revealed the formation of hexanuclear organoantimony(V) based oxo clusters [(-ClCHSb)V(O)(μ-O)(μ-O)(-BuPO)(μ-OCH)] (1), [M(-iPr-CHSb)(μ-O)(μ-O)(μ-OCH)(-BuPO)(py)]·CHOH, where M = Mn, = 2 (2), Co, = 1 (3), Ni, = 2 (4) and Cu, = 2 (5).

In situ generated polysiloxanes stabilizing μ3-oxo bridged Sb3 triangles.

The reaction of RSbO3H2 with t-butylsilanetriol has led to the isolation of organoantimony(v) based molecular triangles stabilized by siloxane frameworks. Depending on the reaction conditions employed or the substituents present on the antimony atom, either a combination of a disiloxane and a tetrasiloxane framework or a trisiloxane framework was generated in situ leading to the stabilization of the Sb3 triangle.

Monoorganoantimony(v) phosphonates and phosphoselininates.

Molecular oxo-hydroxo clusters have been synthesized by reactions of arylstibonic acids with organophosphonic acid and phenylseleninic acid. Single crystal X-ray structural elucidation revealed the formation of [(p-i-PrC6H4Sb)4(OH)4(t-BuPO3)6] (1), [(p-t-BuC6H4Sb)4(O)2(PhPO3)4(PhPO3H)4] (2), [(p-i-PrC6H4Sb)4(O)3(OH)(PhSeO2)2(t-BuPO3)4(t-BuPO3H2)2] (3), [(p-MeC6H4Sb)4(O)3(OH)(PhSeO2)2(t-BuPO3)4(t-BuPO3H2)2] (4) and [(p-t-BuC6H4Sb)2(O) (PhSeO2)2(t-BuPO3H)4] (5) respectively. Mass spectral studies reveal that the clusters maintain their structural integrity in solution as well.