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Contrasting Structure-Directing Effects in the Uranyl-Phthalate/Isophthalate Isomer Systems

Pierre Thuéry 1, * Jack Harrowfield 2, * 
* Corresponding author
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
Abstract : Reaction of uranyl cations with phthalic (H2pht) or isophthalic (H2ipht) acids under solvohydrothermal conditions was performed in the presence of 3d-block metal cations associated with chelating nitrogen donors to give nine zero-, mono-, and diperiodic complexes. [UO2(pht)2Zn(phen)2]2·4H2O (1), where phen is 1,10-phenanthroline, is a heterometallic, tetranuclear complex, while the counterion separation in [Ni(bipy)3][UO2(pht)(NO3)]2 (2), where bipy is 2,2′-bipyridine, yields a monoperiodic, helical uranyl ion complex crystallizing in a pure enantiomeric form. The diperiodic network in [Ni(phen)3][(UO2)3(O)(pht)3]·6H2O (3) displays pseudotrigonal, cuplike cavities containing part of the bulky counterions. [(UO2)2(O)(pht)2Ni(cyclam)(H2O)]2·H2O (4), where cyclam is 1,4,8,11-tetraazacyclotetradecane, is a discrete, bis(μ3-oxo)-bridged tetranuclear uranyl complex of common geometry, to which two Ni(cyclam)2+ moieties are attached through oxo bonding to uranyl. Separation of the 3d-block metal ion complex in [Ni(cyclam)]2[(UO2)7(pht)8(NO3)2] (5) and [Cu(R,S-Me6cyclam)][(UO2)5(O)2(pht)4(H2O)2]·4H2O (6), where R,S-Me6cyclam is 7(R),14(S)-5,5,7,12,12,14-hexamethylcyclam, results in the formation of quasi-planar diperiodic networks hydrogen bonded to the counterions. The three isophthalate complexes [(UO2)2(ipht)3Cu(bipy)2]·H2O (7), [(UO2)2(ipht)2(HCOO)2Ni(cyclam)] (8), and [(UO2)2(ipht)2(HCOO)2Cu(R,S-Me6cyclam)] (9) crystallize as heterometallic diperiodic species with Cu(bipy)22+ being only decorating in 7, while Ni2+ and Cu2+ in 8 and 9 bridge uranyl-containing chains into a network with a V2O5 topology.
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Submitted on : Wednesday, April 21, 2021 - 9:29:55 AM
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Pierre Thuéry, Jack Harrowfield. Contrasting Structure-Directing Effects in the Uranyl-Phthalate/Isophthalate Isomer Systems. Crystal Growth & Design, In press, 21 (5), pp.3000-3013. ⟨10.1021/acs.cgd.1c00158⟩. ⟨cea-03203807⟩



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