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Contrasting networks and entanglements in uranyl ion complexes with adipic and $trans,trans$-Muconic acids

Pierre Thuéry 1 Jack Harrowfield 2 
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 : Adipic (hexane-1,6-dicarboxylic, adpH2) and trans,trans-muconic (trans,trans-hexa-2,4-diene-1,6-dicarboxylic, mucH2) acids have been reacted with uranyl cations under solvo-hydrothermal conditions, yielding nine homo- or heterometallic complexes displaying in their crystal structure the effects of the different flexibility of the ligands. The complexes [PPh4]2[(UO2)2(adp)3] (1) and [Ni(bipy)3][(UO2)2(muc)3]·5H2O (2), where bipy is 2,2′-bipyridine, crystallize as diperiodic networks with the hcb topology, the layers being strongly puckered or quasiplanar, respectively. Whereas [(UO2)2(adp)3Ni(cyclam)]·2H2O (3), where cyclam is 1,4,8,11-tetraazacyclotetradecane, crystallizes as a diperiodic network, [(UO2)2(muc)3Ni(cyclam)]·2H2O (4) is a triperiodic framework in which the NiII cations are introduced as pillars within a uranyl–muc2– framework with the mog topology. [UO2(adp)(HCOO)2Cu(R,S-Me6cyclam)]·2H2O (5), where R,S-Me6cyclam is 7(R),14(S)-5,5,7,12,12,14-hexamethylcyclam, is a diperiodic assembly with the sql topology, and it crystallizes together with [H2NMe2]2[(UO2)2(adp)3] (6), a highly corrugated hcb network with a square-wave profile, which displays 3-fold parallel interpenetration. In contrast, [(UO2)3(muc)2(O)2Cu(R,S-Me6cyclam)] (7) is a diperiodic assembly containing hexanuclear, μ3-oxido-bridged secondary building units which are the nodes of a network with the hxl topology. The two related complexes [PPh3Me]2[(UO2)2(adp)3]·4H2O (8) and [PPh3Me]2[(UO2)2(muc)3]·H2O (9) crystallize as hcb networks, but their different shapes, undulated or quasiplanar, respectively, result in different entanglements, 2-fold parallel interpenetration in 8 and 2-fold inclined 2D → 3D polycatenation in 9.
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Submitted on : Monday, January 31, 2022 - 1:34:32 PM
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Pierre Thuéry, Jack Harrowfield. Contrasting networks and entanglements in uranyl ion complexes with adipic and $trans,trans$-Muconic acids. Inorganic Chemistry, American Chemical Society, 2022, 61 (6), pp.2790-2803. ⟨10.1021/acs.inorgchem.1c03168⟩. ⟨cea-03549299⟩



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