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Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties
Author(s) -
Rogachev Alexander V.,
Gushchin Artem L.,
Abramov Pavel A.,
Kozlova Ekaterina A.,
Vicent Cristian,
Piryazev Dmitry,
Barlow Adam,
Samoc Marek,
Humphrey Mark G.,
Llusar Rosa,
Fedin Vladimir P.,
Sokolov Maxim N.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500319
Subject(s) - chemistry , diimine , niobium , photocatalysis , crystallography , pyridine , bipyridine , crystal structure , ligand (biochemistry) , medicinal chemistry , photochemistry , inorganic chemistry , catalysis , organic chemistry , biochemistry , receptor
Abstract Substitution reactions of binuclear niobium cluster anion [Nb 2 S 4 (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 [Nb 2 S 4 (NCS) 6 L] 2– have been isolated. In the case of 1,10‐phenanthroline and 2‐(2‐pyridyl)benzimidazole (Hpbz), both mono‐ and disubstituted complexes, [Nb 2 S 4 (NCS) 6 L] 2– and [Nb 2 S 4 (NCS) 4 L 2 ], respectively, have been obtained. Crystal structures of (Et 4 N) 2 [Nb 2 S 4 (NCS) 6 (bipy)] · 0.5bipy · 0.7CH 3 CN and [Nb 2 S 4 (pbmz) 2 (NCS) 4 ] · 5DMF · 0.8H 2 O have been determined. All compounds have been characterized by NMR, ESI mass spectrometry, IR, UV/Vis spectroscopy, and CV. TiO 2 nanoparticles modified with (Et 4 N) 2 [Nb 2 S 4 (NCS) 6 (bipy)] show moderate photocatalytic activity in the reaction of H 2 generation from water in the presence of Na 2 S/Na 2 SO 3 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.