New Transition Metal Oxo‐Thiostannate: Synthesis, Characterization, and Investigation of its Photocatalytic Properties

Abstract

The new transition metal oxo‐thiostannate {[Ni(cyclen)]6[Sn6S12O2(OH)6]}·2(ClO4)·19H2O (1) was prepared under hydrothermal conditions using Na4SnS4·14H2O and [Ni(cyclen)](ClO4)2 as reactants. In the crystal structure the rare [Sn6S12O2(OH)6]10– anion is observed, which is composed of SnS2O(OH)3 and SnS4O2 octahedra, and SnS4 tetrahedra sharing edges and corners. The anion is expanded by six Ni2+ centered complexes via Ni–S and Ni–OH bonds. The photocatalytic properties for the visible light driven hydrogen evolution reaction shows that 26.6 mmol·g–1 H2 were evolved after 3 h.

Room Temperature Synthesis of New Thiostannates by Slow Interdiffusion of Different Solvents

“…[4] Recently, we explored solvothermal syntheses using different thiostannate sources and transition metal complexes as reactants for the generation of thiostannates. For example, the reaction of [5] { [6] and [7] (cyclen = 1,4,7,10-tetraazacyclododecane). In another room temperature based synthesis approach,…”

“…Supporting Information (see footnote on the first page of this article): Single crystal data, X-ray powder patterns, EDX data, Tables with bond lengths and angles, [6,7] Cyclen is a tetraaza macrocyclic ligand that usually generates TM n+ complexes with two free coordination sites allowing S 2of the thiostannate anion to coordinate to the TM n+ centers. This is indeed observed in the structure of…”

The First Thiostannate Compound with Copper(II) Synthesized Under Ambient Conditions: Crystal Structure, Electronic and Thermal Properties

“…Applying Na 4 SnS 4 · 14H 2 O as precursor the addition of amine is not necessary, and recently we have shown that [SnS 4 ] 4– condenses very fast to form [Sn 2 S 6 ] 4– units under release of H 2 S , . Reacting [Ni(cyclen)](ClO 4 ) 2 (cyclen = 1,4,7,10‐tetrazacyclododecane) and Na 4 SnS 4 · 14H 2 O under hydrothermal conditions we successfully prepared {[Ni(cyclen)] 6 [Sn 6 S 12 O 2 (OH) 6 ]} · 2(ClO 4 ) · 19H 2 O . Cyclen is a tetraaza macrocyclic ligand that forms TM n+ centred complexes with two free coordination sites and if TM n+ prefers an octahedral coordination, bond formation to thiostannate anions is possible, which is observed in the structure where [Ni(cyclen)] 2+ cations are bound to the central core unit via S 2– and OH – anions .…”

“…Reacting [Ni(cyclen)](ClO 4 ) 2 (cyclen = 1,4,7,10‐tetrazacyclododecane) and Na 4 SnS 4 · 14H 2 O under hydrothermal conditions we successfully prepared {[Ni(cyclen)] 6 [Sn 6 S 12 O 2 (OH) 6 ]} · 2(ClO 4 ) · 19H 2 O . Cyclen is a tetraaza macrocyclic ligand that forms TM n+ centred complexes with two free coordination sites and if TM n+ prefers an octahedral coordination, bond formation to thiostannate anions is possible, which is observed in the structure where [Ni(cyclen)] 2+ cations are bound to the central core unit via S 2– and OH – anions . Encouraged by this observation we used in the present work the [Cu(cyclam)] 2+ complex with a planar environment around Cu(II) and the two apical positions are free for bond formation.…”

Room‐Temperature Solid‐State Transformation of Na4SnS4 ⋅ 14H2O into Na4Sn2S6 ⋅ 5H2O: An Unusual Epitaxial Reaction Including Bond Formation, Mass Transport, and Ionic Conductivity

“…The structural versatility is due to the variable coordination number (CN=4–6) as well as the variable oxidation state of Sn. We recently identified Na 4 SnS 4 ⋅ 14H 2 O ( I ) [15] as a promising starting material for the preparation of new thiostannates from liquid media [10,11] . These syntheses yield rather complex anionic species instead of the simple SnS 4 4− anion [10,11] .…”