Tri- and tetranuclear molybdenum and tungsten chalcogenide clusters: on the way to new materials and catalysts *

Abstract

Посвящается д.х.н., профессору В.Е. Федорову в связи с его 80-летним юбилеем Суммированы данные по электронному строению, окислительно-восстановительным, магнитным, люминесцентным, нелинейно-оптическим и каталитическим свойствах трех-и четырехъядерных халькогенидных кластеров молибдена и вольфрама. Рассмотрены перспективы применения этого семейства кластерных соединений при создании новых материалов для молекулярной электроники, нелинейной оптики и катализа. Библиографиия-202 ссылки. Ключевые слова: халькогенидные кластеры, молибден, вольфрам, материалы, катализаторы Артем Леонидович Гущин. Доктор химических наук, старший научный сотрудник лаборатории синтеза комплексных соединений Федерального бюджетного учреждения науки Института неорганической химии им. А.В. Николаева Сибирского отделения Российской академии наук (ИНХ СО РАН). Тел.: (383) 3165845. Moб. тел.:

A Novel Niobium Cluster Aqua Ion with Capping μ4‐Se Ligand

“…Two of the Nb atoms are almost in the plane formed by four O atoms, while the remaining two Nb atoms are displaced toward the μ 4 -Se atom. This open basket-like structure was previously established in [Nb 4 (μ 4 -S)(μ 2 -O) 5 5 (NCS) 10 ] 6-(2.802-2.867 Å), [13] [Nb 5 (μ 3 -S) 2 (μ 3 -O) 2 (μ 2 -O) 2 (NCS) 14 ] 6-(2.800-2.911 Å), [14] and [Nb 2 S 4 (NCS) 8 ] 4-(2.867 Å). [4] The Nb-Se bond lengths of 2.5310 (18) 4 ].…”

“…The crystal structure was determined for the N-bonded thiocyanate derivative, (PyH) 4.5 [H 1.5 Nb 4 SeO 5 (NCS) 10 ]·0.5H 2 O. The solution properties along with the X-ray structure analysis supports the existence of a {Nb 4 (μ 4 -Se)(μ 2 -O) 5 } 4+ cluster core, most likely [Nb 4 (μ 4 -Se)(μ 2 -O) 5 (H 2 O) 10 ] 4+ aqua ion in solution, where all niobium atoms are in the +4 oxidation state. It should be noted that this is the first example of a selenium-containing niobium aqua complex and a rare example of a group 5 metal complex with a bridged μ 4 -Se ligand.…”

“…[29] The electronic spectrum of the yellow-green aqua ion 1 in 2 m HCl is shown in Figure 1. It has characteristic absorption bands in the visible part at λ max (ε /m -1 cm -1 per Nb) = 382 (2350) nm and 575 (170) nm, which are more shifted towards the longer wavelengths in comparison to the sulfide analog [Nb 4 (μ 4 -S)(μ 2 -O) 5 (H 2 O) 10 ] 4+ (λ max = 369 and 555 nm). [13] The aqua ion is unstable with respect to air oxidation, and smell 10 ] 4+ (dashed line) [14] in 2 m HCl.…”

“…[21] Another approach to niobium aqua complexes consists in the reduction of NbCl 5 in ethanol with zinc or aluminum followed by treatment with aqueous acids. In addition to the trinuclear aqua complexes of {Nb 3 XO 3 } type, such as unique organometallic trinuclear niobium cluster complex with unusual perpendicularly coordinated μ 3 -η 2 :η 2 (Ќ)-acetonitrile ligand, [Nb 3 (μ-η 2 :η 2 -NCCH 3 )O 3 (H 2 O) 9 ] 6+ , [16] it gives, in the presence of S 2-, unprecedented tetra-and pentanuclear aqua ions, [Nb 4 (μ 4 -S)(μ 2 -O) 5 (H 2 O) 10 ] 4+ and [Nb 5 (μ 3 -S) 2 14 ] 8+ , which were isolated and characterized in detail, including X-ray structures of their thiocyanate derivatives. [13,14] This opens up exciting possibilities of doing oxosulfido or related niobium cluster chemistry in aqueous solutions.…”

WS2/MoS2 Heterostructures via Thermal Treatment of MoS2 Layers Electrostatically Functionalized with W3S4 Molecular Clusters

“…30 Interestingly, equivalent Mo3S4 clusters can be synthetized and used as thermal precursors of MoS2 layers. 33,34…”