Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters

Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2018, Volume: 57, Number: 4, Pages: 2072–2084 Pages count : DOI: 10.1021/acs.inorgchem.7b02974

Authors

Litvinova Yulia M. ¹ , Gayfulin Yakov M. ¹ , Kovalenko Konstantin A. ^1,2 , Samsonenko Denis G. ^1,2 , van Leusen Jan ³ , Korolkov Ilya V. ^1,2 , Fedin Vladimir P. ^1,2 , Mironov Yuri V. ^1,2

Affiliations

1	Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences
2	Novosibirsk State University
3	Institute of Inorganic Chemistry, RWTH Aachen University

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.

Litvinova Y.M. , Gayfulin Y.M. , Kovalenko K.A. , Samsonenko D.G. , van Leusen J. , Korolkov I.V. , Fedin V.P. , Mironov Y.V.
Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters
Inorganic Chemistry. 2018. V.57. N4. P.2072–2084. DOI: 10.1021/acs.inorgchem.7b02974 WOS Scopus РИНЦ OpenAlex

Submitted:	Nov 22, 2017
Published print:	Feb 5, 2018

Web of science:	WOS:000426014800041
Scopus:	2-s2.0-85042217303
Elibrary:	35488644
OpenAlex:	W2790207730

DB	Citing
OpenAlex	59
Web of science	56
Scopus	58
Elibrary	60