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Pillared MOFs: structure and ring opening polymerization of cyclic esters

Gong, Yi; Cheng, Fei; Chen, Fei; Beamish-Cook, Jethro; Elsegood, Mark R.J.; Elsegood, Mark Robert James; Derbyshire, Max; Rowe, Oliver; Redshaw, Carl


Yi Gong

Fei Cheng

Fei Chen

Jethro Beamish-Cook

Mark R.J. Elsegood

Mark Robert James Elsegood

Max Derbyshire

Oliver Rowe

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Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry


The solvothermal reaction of Zn(NO3)2·6H2O with 5-aminoisophthalic acid and 4,4′-bipyridyl (4,4′-bipy) led to the self-assembly of the known 3-D hybrid H-bonded/covalent structure {[Zn(5-AIP)(4,4′-bipy)0.5]·DMF}n (1·DMF), but with DMF here (rather than H2O as previously): an analogous reaction using the related 4,4′-azopyridine (4,4′-azopy) in place of 4,4′-bipyridyl afforded the structurally related framework {[Zn(5-AIP)(4,4′-azopy)0.5]·0.75DMF}n (2·0.75DMF). Similar solvothermal reactions of Co(NO3)·6H2O, Mn(NO3)·4H2O and Cd(NO3)·4H2O with 5-aminoisophthalate and the potential linkers 4,4′-bipy, 2-di(4-pyridyl)ethylene (DPE), and 4,4′-azopy afforded the porous 3-D structures {[Co2(NO3)2(5-AIP)(4,4′-bipy)2]·2EtOH}n (3·2EtOH), {[Co(5-AIP)(DPE)]·2DMF}n (4·2DMF), {[Co(5-AIP)(4,4′-azopy)]·2DMA}n (5·2DMA), {[Mn(5-AIP)(4,4′-bipy)]·2DMA}n (6·2DMA), {[Mn(5-AIP)(DPE)]·6DMF}n (7·6DMF), {[Mn(5-AIP)(4,4′-azopy)]·2.5DMF}n (8·2.5DMF), the previously reported {[Cd(5-AIP)(4,4′-bipy)]·3DMF}n (9·3DMF), {[Cd(5-AIP)(DPE)]·DMF}n (10), and {Cd(5-AIP)(4,4′-azopy)(DMF)}n (11), with structures 4-10 bearing the same network topologies with metal atoms and 5-AIP ligands in sheets, bipy ligands acting as pillars, and solvent molecules of crystallisation located around the bipy ligands. The activated MOFs were employed as catalysts for the ring opening polymerization (ROP) of ϵ-caprolactone and δ-valerolactone. ROPs were conducted as melts, and under N2 only 1 with δ-VL (∼93% conversion) was active. In the case of ϵ-CL under air, all the systems were active with 1, 2, and 11 affording >90% conversion. Molecular weights (Mn) were in the range 3760-17 940 Da and the products formed were identified as both cyclic and linear PCL. For δ-VL, the catalysts performed somewhat better, with all systems (except 8) affording ∼90% conversion or more under air. Molecular weights (Mn) were in the range 2180-7940 and as for PCL, the products formed were identified as both cyclic and linear PCL.


Gong, Y., Cheng, F., Chen, F., Beamish-Cook, J., Elsegood, M. R., Elsegood, M. R. J., …Redshaw, C. (2023). Pillared MOFs: structure and ring opening polymerization of cyclic esters. CrystEngComm, 25(2), 267-283.

Journal Article Type Article
Acceptance Date Nov 24, 2022
Online Publication Date Nov 25, 2022
Publication Date Jan 14, 2023
Deposit Date Nov 25, 2022
Publicly Available Date Jan 3, 2023
Journal CrystEngComm
Electronic ISSN 1466-8033
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 25
Issue 2
Pages 267-283
Keywords Condensed Matter Physics; General Materials Science; General Chemistry
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