Octahedral cyanohydroxo cluster complex trans-[Re6Se 8(CN)4(OH)2]4-: Synthesis, crystal structure, and properties

Yuri V. Mironov; Konstantin A. Brylev; Sung Jin Kim; Svetlana G. Kozlova; Noboru Kitamura; Vladimir E. Fedorov

doi:10.1016/j.ica.2011.01.110

Octahedral cyanohydroxo cluster complex trans-[Re₆Se ₈(CN)₄(OH)₂]^4-: Synthesis, crystal structure, and properties

Yuri V. Mironov, Konstantin A. Brylev, Sung Jin Kim, Svetlana G. Kozlova, Noboru Kitamura, Vladimir E. Fedorov

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

A hexarhenium cyanohydroxo anionic cluster complex [Re₆Se ₈(CN)₄(OH)₂]^4- was synthesized for the first time starting from [Re₆Se₈(OH)₆] ^4-, which was crystallized as a salt of the composition Cs _2.75K_1.25[Re₆Se₈(CN) ₄(OH)₂]·H₂O (1). The reaction of the complex with Cu²⁺ in an aqueous ammonia or methylamine solutions afforded [Cu(NH₃)₅]₂[Re₆Se ₈(CN)₄(OH)₂]·8H₂O (2) or [{Cu(CH₃NH₂)₄}₂Re₆Se ₈(CN)₄(OH)₂] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) , c = 19.430(2) , V = 5938.3(10) ³); compound 2 is crystallized in the monoclinic space group P2 ₁/n with two formula units per cell (a = 12.1845(13) , b = 8.6554(9) , c = 19.2568(19) , β = 91.081(2)°, V = 2030.5(4) ³); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) , b = 14.611(3) , c = 13.751(3) , V = 3981.2(13) ³). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re₆Se₈(CN)₄(OH)₂]^4- was elucidated by DFT calculations.

Original language	English
Pages (from-to)	363-368
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	370
Issue number	1
DOIs	https://doi.org/10.1016/j.ica.2011.01.110
State	Published - 15 May 2011

Bibliographical note

Funding Information:
This research was supported by the Russian Foundation for Basic Research (Grant Nos. 08-03-00267, 09-03-92004), Interdisciplinary Grant No. 76 and by the State Contract No. 02.740.11.0628. Also K. A. Brylev thanks the Japan Society for the Promotion of Science (JSPS) for a Post Doctoral Fellowship for Foreign Researchers.

Keywords

Cluster compounds
Crystal structure
Electronic structure
Luminescence
Rhenium

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10.1016/j.ica.2011.01.110

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title = "Octahedral cyanohydroxo cluster complex trans-[Re6Se 8(CN)4(OH)2]4-: Synthesis, crystal structure, and properties",

abstract = "A hexarhenium cyanohydroxo anionic cluster complex [Re6Se 8(CN)4(OH)2]4- was synthesized for the first time starting from [Re6Se8(OH)6] 4-, which was crystallized as a salt of the composition Cs 2.75K1.25[Re6Se8(CN) 4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se 8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se 8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) , c = 19.430(2) , V = 5938.3(10) 3); compound 2 is crystallized in the monoclinic space group P2 1/n with two formula units per cell (a = 12.1845(13) , b = 8.6554(9) , c = 19.2568(19) , β = 91.081(2)°, V = 2030.5(4) 3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) , b = 14.611(3) , c = 13.751(3) , V = 3981.2(13) 3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4- was elucidated by DFT calculations.",

keywords = "Cluster compounds, Crystal structure, Electronic structure, Luminescence, Rhenium",

author = "Mironov, {Yuri V.} and Brylev, {Konstantin A.} and Kim, {Sung Jin} and Kozlova, {Svetlana G.} and Noboru Kitamura and Fedorov, {Vladimir E.}",

note = "Funding Information: This research was supported by the Russian Foundation for Basic Research (Grant Nos. 08-03-00267, 09-03-92004), Interdisciplinary Grant No. 76 and by the State Contract No. 02.740.11.0628. Also K. A. Brylev thanks the Japan Society for the Promotion of Science (JSPS) for a Post Doctoral Fellowship for Foreign Researchers. ",

year = "2011",

month = may,

day = "15",

doi = "10.1016/j.ica.2011.01.110",

language = "English",

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journal = "Inorganica Chimica Acta",

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TY - JOUR

T1 - Octahedral cyanohydroxo cluster complex trans-[Re6Se 8(CN)4(OH)2]4-

T2 - Synthesis, crystal structure, and properties

AU - Mironov, Yuri V.

AU - Brylev, Konstantin A.

AU - Kim, Sung Jin

AU - Kozlova, Svetlana G.

AU - Kitamura, Noboru

AU - Fedorov, Vladimir E.

N1 - Funding Information: This research was supported by the Russian Foundation for Basic Research (Grant Nos. 08-03-00267, 09-03-92004), Interdisciplinary Grant No. 76 and by the State Contract No. 02.740.11.0628. Also K. A. Brylev thanks the Japan Society for the Promotion of Science (JSPS) for a Post Doctoral Fellowship for Foreign Researchers.

PY - 2011/5/15

Y1 - 2011/5/15

N2 - A hexarhenium cyanohydroxo anionic cluster complex [Re6Se 8(CN)4(OH)2]4- was synthesized for the first time starting from [Re6Se8(OH)6] 4-, which was crystallized as a salt of the composition Cs 2.75K1.25[Re6Se8(CN) 4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se 8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se 8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) , c = 19.430(2) , V = 5938.3(10) 3); compound 2 is crystallized in the monoclinic space group P2 1/n with two formula units per cell (a = 12.1845(13) , b = 8.6554(9) , c = 19.2568(19) , β = 91.081(2)°, V = 2030.5(4) 3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) , b = 14.611(3) , c = 13.751(3) , V = 3981.2(13) 3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4- was elucidated by DFT calculations.

AB - A hexarhenium cyanohydroxo anionic cluster complex [Re6Se 8(CN)4(OH)2]4- was synthesized for the first time starting from [Re6Se8(OH)6] 4-, which was crystallized as a salt of the composition Cs 2.75K1.25[Re6Se8(CN) 4(OH)2]·H2O (1). The reaction of the complex with Cu2+ in an aqueous ammonia or methylamine solutions afforded [Cu(NH3)5]2[Re6Se 8(CN)4(OH)2]·8H2O (2) or [{Cu(CH3NH2)4}2Re6Se 8(CN)4(OH)2] (3), respectively. All of these three compounds were characterized by a single-crystal X-ray diffraction method. Compound 1 is crystallized in the tetragonal space group I4/m with eight formula units per cell (a = b = 17.4823(14) , c = 19.430(2) , V = 5938.3(10) 3); compound 2 is crystallized in the monoclinic space group P2 1/n with two formula units per cell (a = 12.1845(13) , b = 8.6554(9) , c = 19.2568(19) , β = 91.081(2)°, V = 2030.5(4) 3); compound 3 is crystallized in the orthorhombic space group Cmcm with four formula units per cell (a = 19.816(4) , b = 14.611(3) , c = 13.751(3) , V = 3981.2(13) 3). The luminescence properties of 1 were studied in both aqueous solution and solid state. In addition, the electronic structure of [Re6Se8(CN)4(OH)2]4- was elucidated by DFT calculations.

KW - Cluster compounds

KW - Crystal structure

KW - Electronic structure

KW - Luminescence

KW - Rhenium

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