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Title: Use of multiple functionalised ligand sets in metalorganic framework formation : synthesis, characterisation and gas uptake studies
Author: Rowe, Oliver
Awarding Body: University of East Anglia
Current Institution: University of East Anglia
Date of Award: 2013
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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.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available