Use of multiple functionalised ligand sets in metalorganic framework formation: synthesis, characterisation and gas uptake studies

Rowe, Oliver (2013) Use of multiple functionalised ligand sets in metalorganic framework formation: synthesis, characterisation and gas uptake studies. Doctoral thesis, University of East Anglia.

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Abstract

Abstract
A variety of metal-organic frameworks have been synthesised and structurally
characterised and their gas uptake behaviours investigated.
The solvothermal reaction of Zn(NO3)2.6H2O with 5-aminoisophthalic acid (H2-5-
AIP) and 4,4'-bipyridyl (4,4'-bipy) led to the self-assembly of the 3D hybrid Hbonded/
covalent structure {[Zn(5-AIP)(4,4'-bipy)0.5].DMF}n (1), with an analogous
reaction using the related molecule 4,4'-azopyridine (4,4'-azopy) in place of 4,4'-bipy
giving the isostructural framework {[Zn(5-AIP)(4,4'-azopy)0.5].DMF}n (2). Similar
solvothermal reactions of Co(NO3).6H2O, Mn(NO3).4H2O and Cd(NO3).4H2O with
5-aminoisophthalate and the potential linkers 4,4'-bipy, 1,2-di(4-pyridyl)ethylene
(DPE) and 4,4'-azopy afforded the porous 3D structures {[Co2(NO3)2(5-AIP)(4,4'-
bipy)2].2EtOH}n (3), {[Co(5-AIP)(DPE)].3DMF}n (4), {[Co(5-AIP)(4,4'-
azopy)].2DMA}n (5), {[Mn(5-AIP)(4,4'-bipy)].2DMA}n (6), {[Mn(5-
AIP)(DPE)].1.5DMF}n (7), {[Mn(5-AIP)(4,4'-azopy)].1.5DMF}n (8), {[Cd(5-
AIP)(4,4'-bipy)].3DMF}n (9), {[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
topology. Carbon dioxide uptakes for these structures, whilst modest, reveal an
interesting pattern, with enhanced uptakes observed for those structures which bear
larger pore sizes and polar functionalities.
Hydrothermal reactions of the reduced Schiff base 4-carboxy-phenylenemethyleneamino-
4-benzoic acid (L1H2) with Zn(OH)2 and DPE afforded a nonporous
2D coordination polymer of the formula {[Zn2(L1)2(DPE)].H2O}n, (12) with
the analogous reaction of L1H2 with Zn(OH)2 and 4,4'-azopy giving the porous 3D
structure {[Zn3(L1)3(4,4'-azopy)].7.5H2O}n (13), which exhibits interesting hysteretic
behaviour on CO2 adsorption and desorption.
Lower-rim acid functionalised calix[4]arene structures (14, 15) were prepared by the
reaction of 25,27-bis(methoxycarboxylic acid)-26,28-dihydroxycalix[4]arene (L2H2)
coordination polymers with Li2CO3 and tert-butyllithium respectively, with the
solvothermal reaction of L2H2 with zinc nitrate affording the 1D coordination
polymer of {[Zn(L2)2](DMF)(H2O)}n (16). Solvothermal reactions of the related
calix[4]arene molecule 25,27-bis(methoxycarboxylic acid)-26,28-dihydroxy-4-
tertbutylcalix[4]arene (L3H2) with Zn(NO3)2.6H2O and 4,4'-bipy, DPE and 4,4'-
ii
azopy gave a series of 2D structures of the formulae {[Zn(4,4'-bipy)(L3)].2.25DEF}n
(17), {[Zn2(L3)(DPE)].DEF}n (18) and {[Zn(OH2)2(L3)(4,4'-azopy)].DEF}n (19).
The structures have been fully characterised and their porosities investigated using
TGA.

Item Type: Thesis (Doctoral)
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Mia Reeves
Date Deposited: 05 Mar 2014 11:27
Last Modified: 05 Mar 2014 11:27
URI: https://ueaeprints.uea.ac.uk/id/eprint/47912
DOI:

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