%0 Journal Article %T Functionalized Aromatic Dicarboxylate Ligands in Uranyl–Organic Assemblies: The Cases of Carboxycinnamate and 1,2-/1,3-Phenylenedioxydiacetate %+ Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE) %+ Institut de Science et d'ingénierie supramoléculaires (ISIS) %A Thuéry, Pierre %A Atoini, Youssef %A Harrowfield, Jack %< avec comité de lecture %@ 0020-1669 %J Inorganic Chemistry %I American Chemical Society %V 59 %P 2923-2936 %8 2020-02-17 %D 2020 %R 10.1021/acs.inorgchem.9b03273 %Z Chemical Sciences/Cristallography %Z Chemical Sciences/Coordination chemistryJournal articles %X 2-Carboxycinnamic acid (ccnH$_2$) and the isomeric 1,2-and 1,3-phenylenedioxydiacetic acids (1,2-and 1,3-pddaH$_2$) have been used to synthesize eight uranyl ion complexes under solvo-hydrothermal conditions. In the four complexes [PPh$_4$]$_2$[UO$_2$(ccn)(NO$_3$)]$_2$, [PPh$_4$]$_2$[UO$_2$(ccn)(dibf)]$_2$ , [UO$_2$(ccn)(bipy)]$_2$, and [Ni(R,S-Me$_6$cyclam)][UO$_2$(ccn)(HCOO)]$_2$ , the ccn$^{2-}$ dianion retains a nearly planar geometry, which favors the formation of the centrosymmetric [UO2(ccn)]2 dimeric unit. Additional terminal ligands, either neutral (bipy = 2,2ʹ-bipyridine) or anionic (nitrate, dibf-= 1,3-dihydro-3-oxo-1-isobenzofuranacetate, and formate, the two latter formed in situ) complete the uranyl coordination sphere, leading in all cases to discrete, dinuclear species. Sodium(I) bonding to the carboxylate/ether O$_4$ site of the 1,2-pdda$^{2-}$ dianion in the two complexes [UO$_2$Na(1,2-pdda)(OH)] and [(UO$_2$)$_2$Na$_2$(1,2-pdda)$_2$(C2O$_4$)] results in this ligand being planar. Further lateral coordination to uranyl and sodium bonding to a uranyl oxo group allow formation of heterometallic diperiodic networks containing monoperiodic uranyl-only subunits. In the absence of Na$^+$ cations, 1,2-pdda$^{2-}$ adopts a conformation in which one carboxylate group is tilted out of the ligand plane in [UO$_2$(1,2-pdda)$_2$Ni(cyclam)], and diaxial carboxylato bonding to nickel(II) unites uranyl-only monoperiodic subunits into a diperiodic network. The 1,3-pdda$^{2-}$ ligand in [UO$_2$(1,3-pdda)(H$_2$O)] is also non-planar with one tilted carboxylate group, and the bridging bidentate nature of both carboxylate groups allows formation of a triperiodic framework in which both metal and ligand are four-coordinated nodes. While the emission spectra of complexes 1 and 5 display the vibronic progression considered typical of uranyl ion, those of complexes 2, 4 and 8 show broad emission bands which in the case of complex 4 completely replace the uranyl emissions and which appear to be ligand-centred. The low energy of these broad bands can be rationalized in terms of the close association of certain ligand pairs within the structures. %G English %2 https://cea.hal.science/cea-02485715/document %2 https://cea.hal.science/cea-02485715/file/Thuery_InorgChem1_2020_V0.pdf %L cea-02485715 %U https://cea.hal.science/cea-02485715 %~ CEA %~ CNRS %~ UNIV-STRASBG %~ PUBNIMBE %~ DSV %~ INC-CNRS %~ IRAMIS-NIMBE %~ CEA-UPSAY %~ UNIV-PARIS-SACLAY %~ CEA-DRF %~ SITE-ALSACE %~ TEST-HALCNRS %~ UNIVERSITE-PARIS-SACLAY %~ GS-ENGINEERING %~ IRAMIS %~ GS-CHIMIE %~ GS-PHYSIQUE %~ INSTITUT-SCIENCES-LUMIERE