Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

Alexander Rogachev; Artem Gushchin; Pavel Abramov; Ekaterina Kozlova; Cristian Vicent; Dmitry Piryazev; Adam Barlow; Marek Samoc; Mark Humphrey; Rosa Llusar; Vladamir Fedin; Maxim Sokolov

doi:10.1002/ejic.201500319

Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

Alexander Rogachev, Artem Gushchin, Pavel Abramov, Ekaterina Kozlova, Cristian Vicent, Dmitry Piryazev, Adam Barlow, Marek Samoc, Mark Humphrey, Rosa Llusar, Vladamir Fedin, Maxim Sokolov

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Abstract

Substitution reactions of binuclear niobium cluster anion [Nb<inf>2</inf>S<inf>4</inf>(NCS)<inf>8</inf>]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<inf>2</inf>S<inf>4</inf>(NCS)<inf>6</inf>L]2- have been isolated. In the case of 1,10-phenanthroline and 2-(2-pyridyl)benzimidazole (Hpbz), both mono- and disubstituted complexes, [Nb<inf>2</inf>S<inf>4</inf>(NCS)<inf>6</inf>L]2- and [Nb<inf>2</inf>S<inf>4</inf>(NCS)<inf>4</inf>L<inf>2</inf>], respectively, have been obtained. Crystal structures of (Et<inf>4</inf>N)<inf>2</inf>[Nb<inf>2</inf>S<inf>4</inf>(NCS)<inf>6</inf>(bipy)]Â·0.5bipyÂ·0.7CH<inf>3</inf>CN and [Nb<inf>2</inf>S<inf>4</inf>(pbmz)<inf>2</inf>(NCS)<inf>4</inf>]Â·5DMFÂ·0.8H<inf>2</inf>O have been determined. All compounds have been characterized by NMR, ESI mass spectrometry, IR, UV/Vis spectroscopy, and CV. TiO<inf>2</inf> nanoparticles modified with (Et<inf>4</inf>N)<inf>2</inf>[Nb<inf>2</inf>S<inf>4</inf>(NCS)<inf>6</inf>(bipy)] show moderate photocatalytic activity in the reaction of H<inf>2</inf> generation from water in the presence of Na<inf>2</inf>S/Na<inf>2</inf>SO<inf>3</inf> 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.

Original language	English
Pages (from-to)	2865-2874
Journal	European Journal of Inorganic Chemistry
Volume	2015
Issue number	17
DOIs	https://doi.org/10.1002/ejic.201500319
Publication status	Published - 2015

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Rogachev, A., Gushchin, A., Abramov, P., Kozlova, E., Vicent, C., Piryazev, D., Barlow, A., Samoc, M., Humphrey, M., Llusar, R., Fedin, V., & Sokolov, M. (2015). Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties. European Journal of Inorganic Chemistry, 2015(17), 2865-2874. https://doi.org/10.1002/ejic.201500319

@article{c90031f492d940d1a3b46b97fa93b4ab,

title = "Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties",

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)]{\^A}·0.5bipy{\^A}·0.7CH3CN and [Nb2S4(pbmz)2(NCS)4]{\^A}·5DMF{\^A}·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.",

author = "Alexander Rogachev and Artem Gushchin and Pavel Abramov and Ekaterina Kozlova and Cristian Vicent and Dmitry Piryazev and Adam Barlow and Marek Samoc and Mark Humphrey and Rosa Llusar and Vladamir Fedin and Maxim Sokolov",

year = "2015",

doi = "10.1002/ejic.201500319",

language = "English",

volume = "2015",

pages = "2865--2874",

journal = "European Journal of Inorganic Chemistry",

publisher = "Wiley-VCH Verlag GmbH",

number = "17",

}

Rogachev, A, Gushchin, A, Abramov, P, Kozlova, E, Vicent, C, Piryazev, D, Barlow, A, Samoc, M, Humphrey, M, Llusar, R, Fedin, V & Sokolov, M 2015, 'Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties', European Journal of Inorganic Chemistry, vol. 2015, no. 17, pp. 2865-2874. https://doi.org/10.1002/ejic.201500319

TY - JOUR

T1 - Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

AU - Rogachev, Alexander

AU - Gushchin, Artem

AU - Abramov, Pavel

AU - Kozlova, Ekaterina

AU - Vicent, Cristian

AU - Piryazev, Dmitry

AU - Barlow, Adam

AU - Samoc, Marek

AU - Humphrey, Mark

AU - Llusar, Rosa

AU - Fedin, Vladamir

AU - Sokolov, Maxim

PY - 2015

Y1 - 2015

N2 - 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)]Â·0.5bipyÂ·0.7CH3CN and [Nb2S4(pbmz)2(NCS)4]Â·5DMFÂ·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.

AB - 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)]Â·0.5bipyÂ·0.7CH3CN and [Nb2S4(pbmz)2(NCS)4]Â·5DMFÂ·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.

U2 - 10.1002/ejic.201500319

DO - 10.1002/ejic.201500319

M3 - Article

VL - 2015

SP - 2865

EP - 2874

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 17

ER -

Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

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