Structural Dynamics and Adsorption Properties of the Breathing Microporous Aliphatic Metal–Organic Framework

Structural Dynamics and Adsorption Properties of the Breathing Microporous Aliphatic Metal–Organic Framework Full article

Journal

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

Output data

Year: 2020, Volume: 59, Number: 21, Pages: 15724-15732 Pages count : 9 DOI: 10.1021/acs.inorgchem.0c02125

Authors

Demakov Pavel A. ^1,2 , Poryvaev Artem S. ^2,3 , Kovalenko Konstantin A. ^1,2 , Samsonenko Denis G. ^1,2 , Fedin Matvey V. ^2,3 , Fedin Vladimir P. ^1,2 , Dybtsev Danil N. ^1,2

Affiliations

1	Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Ave., Novosibirsk 630090, Russia
2	Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Ave., Novosibirsk 630090, Russia
3	International Tomography Center SB RAS, 3a Institutskaya St., Novosibirsk 630090, Russia

A mixed-ligand metal–organic framework [Zn2(chdc)2(dabco)]·2NMP (chdc2– = trans-1,4-cyclohexanedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane; NMP = N-methylpyrrolidone) was synthesized under solvothermal conditions. This coordination compound demonstrates a guest-driven framework breathing due to a conformational change between e,e-chdc and a,a-chdc forms of the linkers with a reversible restoration of crystallinity. Both the local and longer-range coordination environment of the metal centers were extensively studied by electron paramagnetic resonance on a Cu(II)-doped compound. This approach allowed the detailed investigation of the ligand structural conformations and the framework structural dynamics, supported by an X-ray diffraction method. Carbon dioxide and methane adsorption measurements as well as vapor sorption of benzene and cyclohexane at 298 K of the activated compound were studied. While adsorption of small gas molecules, such as CO2, CH4, and N2, is moderate and does not induce the phase transition, the multistepped character of C6H6 and C6H12 adsorption isotherms characterize the breathing nature of [Zn2(chdc)2(dabco)]. The uptake of benzene from the vapor phase reaches 125 mL·g–1 at 298 K, which surpasses most of benzene uptake values reported for microporous metal–organic frameworks.

Demakov P.A. , Poryvaev A.S. , Kovalenko K.A. , Samsonenko D.G. , Fedin M.V. , Fedin V.P. , Dybtsev D.N.
Structural Dynamics and Adsorption Properties of the Breathing Microporous Aliphatic Metal–Organic Framework
Inorganic Chemistry. 2020. V.59. N21. P.15724-15732. DOI: 10.1021/acs.inorgchem.0c02125 WOS Scopus РИНЦ OpenAlex

Submitted:	Jul 17, 2020
Published print:	Oct 12, 2020

Web of science:	WOS:000588738100017
Scopus:	2-s2.0-85094196342
Elibrary:	45215670
OpenAlex:	W3092357072

DB	Citing
Web of science	18
Scopus	19
Elibrary	22
OpenAlex	19