Research output: Contribution to journal › Article › peer-review
Multifunctional Metal-Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters. / Litvinova, Yulia M.; Gayfulin, Yakov M.; Kovalenko, Konstantin A. et al.
In: Inorganic Chemistry, Vol. 57, No. 4, 19.02.2018, p. 2072-2084.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Multifunctional Metal-Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters
AU - Litvinova, Yulia M.
AU - Gayfulin, Yakov M.
AU - Kovalenko, Konstantin A.
AU - Samsonenko, Denis G.
AU - Van Leusen, Jan
AU - Korolkov, Ilya V.
AU - Fedin, Vladimir P.
AU - Mironov, Yuri V.
PY - 2018/2/19
Y1 - 2018/2/19
N2 - The redox-active rhenium octahedral cluster unit [Re6Se8(CN)6]4- was combined with Gd3+ ions and dicarboxylate linkers in novel types of metal-organic frameworks (MOFs) that display a set of functional properties. The hydrolytically stable complexes [{Gd(H2O)3}2(L)Re6Se8(CN)6]·nH2O (1, L = furan-2,5-dicarboxylate, fdc; 2, L = thiophene-2,5-dicarboxylate, tdc) exhibit a 3D framework of trigonal symmetry where 1D chains of [{Gd(H2O)3}2(L)]4+ are connected by [Re6Se8(CN)6]4- clusters. Frameworks contain spacious channels filled with H2O. Solvent molecules can be easily removed under vacuum to produce permanently porous solids with high volumetric CO2 uptake and remarkable CO2/N2 selectivity at room temperature. The frameworks demonstrate an ability for reversible redox transformations of the cluster fragment. The orange powders of compounds 1 and 2 react with Br2, yielding dark-green powders of [{Gd(H2O)3}2(L)Re6Se8(CN)6]Br·nH2O (3, L = fdc; 4, L = tdc). Compounds 3 and 4 are isostructural with 1 and 2 and also have permanently porous frameworks but display different optical, magnetic, and sorption properties. In particular, oxidation of the cluster fragment "switches off" its luminescence in the red region, and the incorporation of Br- leads to a decrease of the solvent-accessible volume in the channels of 3 and 4. Finally, the green powders of 3 and 4 can be reduced back to the orange powders of 1 and 2 by reaction with hydrazine, thus displaying a rare ability for fully reversible chemical redox transitions. Compounds 1-4 are mentioned as a new class of redox-active cluster-based MOFs with potential usage as multifunctional materials for gas separation and chemical contamination sensors.
AB - The redox-active rhenium octahedral cluster unit [Re6Se8(CN)6]4- was combined with Gd3+ ions and dicarboxylate linkers in novel types of metal-organic frameworks (MOFs) that display a set of functional properties. The hydrolytically stable complexes [{Gd(H2O)3}2(L)Re6Se8(CN)6]·nH2O (1, L = furan-2,5-dicarboxylate, fdc; 2, L = thiophene-2,5-dicarboxylate, tdc) exhibit a 3D framework of trigonal symmetry where 1D chains of [{Gd(H2O)3}2(L)]4+ are connected by [Re6Se8(CN)6]4- clusters. Frameworks contain spacious channels filled with H2O. Solvent molecules can be easily removed under vacuum to produce permanently porous solids with high volumetric CO2 uptake and remarkable CO2/N2 selectivity at room temperature. The frameworks demonstrate an ability for reversible redox transformations of the cluster fragment. The orange powders of compounds 1 and 2 react with Br2, yielding dark-green powders of [{Gd(H2O)3}2(L)Re6Se8(CN)6]Br·nH2O (3, L = fdc; 4, L = tdc). Compounds 3 and 4 are isostructural with 1 and 2 and also have permanently porous frameworks but display different optical, magnetic, and sorption properties. In particular, oxidation of the cluster fragment "switches off" its luminescence in the red region, and the incorporation of Br- leads to a decrease of the solvent-accessible volume in the channels of 3 and 4. Finally, the green powders of 3 and 4 can be reduced back to the orange powders of 1 and 2 by reaction with hydrazine, thus displaying a rare ability for fully reversible chemical redox transitions. Compounds 1-4 are mentioned as a new class of redox-active cluster-based MOFs with potential usage as multifunctional materials for gas separation and chemical contamination sensors.
KW - BRIDGED RE(6)Q(8) Q
KW - COORDINATION POLYMERS
KW - CARBON-DIOXIDE
KW - CRYSTAL
KW - HYDRAZINE
KW - COMPLEXES
KW - SE
KW - LUMINESCENCE
KW - ADSORPTION
KW - OXIDATION
UR - http://www.scopus.com/inward/record.url?scp=85042217303&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.7b02974
DO - 10.1021/acs.inorgchem.7b02974
M3 - Article
C2 - 29400450
AN - SCOPUS:85042217303
VL - 57
SP - 2072
EP - 2084
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 4
ER -
ID: 10422224