Binuclear sulfide niobium clusters coordinated by diimine ligands: Synthesis, structure, photocatalytic activity and optical limiting properties

Alexander V. Rogachev, Artem L. Gushchin, Pavel A. Abramov, Ekaterina A. Kozlova, Cristian Vicent, Dmitry Piryazev, Adam Barlow, Marek Samoc, Mark G. Humphrey, Rosa Llusar, Vladimir P. Fedin, Maxim N. Sokolov*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

Substitution reactions of binuclear niobium cluster anion [Nb2S4(NCS)8]4- with different types of pyridine-based diimine ligands have been carried out. In the case of 2,2′-bipyridine (bipy) and its derivatives, only monosubstituted complexes [Nb2S4(NCS)6L]2- have been isolated. In the case of 1,10-phenanthroline and 2-(2-pyridyl)benzimidazole (Hpbz), both mono- and disubstituted complexes, [Nb2S4(NCS)6L]2- and [Nb2S4(NCS)4L2], respectively, have been obtained. Crystal structures of (Et4N)2[Nb2S4(NCS)6(bipy)]·0.5bipy·0.7CH3CN and [Nb2S4(pbmz)2(NCS)4]·5DMF·0.8H2O have been determined. All compounds have been characterized by NMR, ESI mass spectrometry, IR, UV/Vis spectroscopy, and CV. TiO2 nanoparticles modified with (Et4N)2[Nb2S4(NCS)6(bipy)] show moderate photocatalytic activity in the reaction of H2 generation from water in the presence of Na2S/Na2SO3 as a sacrificial electron donor system. The linear and nonlinear optical properties of the complexes with bipyridine ligands have been studied; the complexes function as broad-band optical limiters. A series of complexes, [Nb2S4(NCS)6L]2- and [Nb2S4(NCS)4L2], where L is a bipyridine, phenanthroline or 2-(2-pyridyl)benzimidazole has been prepared. TiO2 nanoparticles modified with (Et4N)2[Nb2S4(NCS)6(bipy)] exhibit photocatalytic activity for H2 generation from water in the presence of a sacrificial electron-donor system. The complexes function as optical limiters.

Original languageEnglish
Pages (from-to)2865-2874
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Volume2015
Issue number17
DOIs
Publication statusPublished - 1 Jun 2015

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