Tailoring Porosity and Rotational Dynamics in a Series of Octacarboxylate Metal-Organic Frameworks | Sciact - CRIS-system of Boreskov Institute of Catalysis

Tailoring Porosity and Rotational Dynamics in a Series of Octacarboxylate Metal-Organic Frameworks Full article

Journal

Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424 , E-ISSN: 1091-6490

Output data

Year: 2017, Volume: 114, Number: 12, Pages: 3056-3061 Pages count : 6 DOI: 10.1073/pnas.1615172114

Tags

CH4, CO2, Copper, Metal-organic framework, Molecular rotors

Authors

Moreau Florian ¹ , Kolokolov Daniil I. ^2,3 , Stepanov Alexander G. ^2,3 , Easun Timothy L. ⁴ , Dailly Anne ⁵ , Lewis William ⁶ , Blake Alexander J. ⁶ , Nowell Harriott ⁷ , Lennox Matthew J. ⁶ , Besley Elena ⁶ , Yang Sihai ¹ , Schröder Martin ^1,8

Affiliations

1	School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
2	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
3	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
4	School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
5	General Motors Global Research and Development Center, Warren, MI, USA
6	School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK
7	Diamond Light Source, Harwell Science Campus, Oxon, OX11 0DE, UK
8	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia

Funding (7)

1	The Ministry of Education and Science of the Russian Federation	14.Z50.31.0006
2	University of Nottingham
3	University of Manchester
4	European Research Council	226593
5	European Research Council	307755 ERC-2012-StG_20111012 FIN
6	Royal Society	IE150114
7	Engineering and Physical Sciences Research Council	EP/I011870

Modulation and precise control of porosity of metal-organic frameworks (MOFs) is of critical importance to their materials function. Here we report modulation of porosity for a series of isoreticular octacarboxylate MOFs, denoted MFM-180 to MFM-185, via a strategy of selective elongation of metal-organic cages. Owing to the high ligand connectivity, these MOFs do not show interpenetration, and are robust structures that have permanent porosity. Interestingly, activated MFM-185a shows a high Brunauer–Emmett–Teller (BET) surface area of 4,734 m2 g−1 for an octacarboxylate MOF. These MOFs show remarkable CH4 and CO2 adsorption properties, notably with simultaneously high gravimetric and volumetric deliverable CH4 capacities of 0.24 g g−1 and 163 vol/vol (298 K, 5–65 bar) recorded for MFM-185a due to selective elongation of tubular cages. The dynamics of molecular rotors in deuterated MFM-180a-d16 and MFM-181a-d16 were investigated by variable-temperature 2H solid-state NMR spectroscopy to reveal the reorientation mechanisms within these materials. Analysis of the flipping modes of the mobile phenyl groups, their rotational rates, and transition temperatures paves the way to controlling and understanding the role of molecular rotors through design of organic linkers within porous MOF materials.

Moreau F. , Kolokolov D.I. , Stepanov A.G. , Easun T.L. , Dailly A. , Lewis W. , Blake A.J. , Nowell H. , Lennox M.J. , Besley E. , Yang S. , Schröder M.
Tailoring Porosity and Rotational Dynamics in a Series of Octacarboxylate Metal-Organic Frameworks

Proceedings of the National Academy of Sciences of the United States of America. 2017. V.114. N12. P.3056-3061. DOI: 10.1073/pnas.1615172114 WOS Scopus РИНЦ AN PMID OpenAlex

Full text from publisher

Submitted:	Sep 10, 2016
Accepted:	Jan 25, 2017
Published online:	Mar 9, 2017
Published print:	Mar 21, 2017

Web of science:	WOS:000396893600049
Scopus:	2-s2.0-85016102050
Elibrary:	29484418
Chemical Abstracts:	2017:399271
PMID:	28280097
OpenAlex:	W2593920839

DB	Citing
Web of science	70
Scopus	68
Elibrary	64
OpenAlex	77