Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks

Moreau, Florian, Kolokolov, Daniil I., Stepanov, Alexander G., Easun, Timothy, Dailly, Anne, Lewis, William, Blake, Alexander J., Nowell, Harriott, Lennox, Matthew J., Besley, Elena, Yang, Sihai and Schröder, Martin 2017. 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 114 (12) , pp. 3056-3061. 10.1073/pnas.1615172114

[img]
Preview
PDF - Accepted Post-Print Version
Download (1MB) | Preview
[img]
Preview
PDF - Supplemental Material
Download (4MB) | Preview

Abstract

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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: National Academy of Sciences
ISSN: 0027-8424
Date of First Compliant Deposit: 9 May 2017
Date of Acceptance: 25 January 2017
Last Modified: 28 Oct 2018 04:39
URI: http://orca.cf.ac.uk/id/eprint/100436

Citation Data

Cited 15 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics