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1,2-, 1,3- and 1,4-Phenylenediacetate Complexes of Uranyl Ion with Additional Metal Cations and/or Ancillary N-Donor Ligands: Confronting Ligand Geometrical Proclivities

Abstract : Fourteen uranyl ion complexes have been obtained from reaction of 1,2-1,3-, or 1,4-phenylenediacetic acids (1,2-1,3-, or 1,4-H$_2$PDA) with uranyl nitrate under solvo-hydrothermal conditions and in the presence of diverse additional metal ions and/or N-donor chelating or macrocyclic species. The complexes [UO$_2$(1,2-PDA)(bipy)].CH$_3$CN (1), [UO$_2$(1,2-PDA)(phen)] (2), [UO$_2$(1,3-PDA)(bipy)] (3), and [UO$_2$(1,3-PDA)(phen)] (4), where bipy = 2,2ʹ-bipyridine and phen = 1,10-phenanthroline, crystallize as simple monoperiodic (1D) coordination polymers with slightly variable geometry and mode of association through weak interactions. Complex 5, [H$_2$-2.2.2][(UO$_2$)$_2$(1,2-PDA)$_3$].CH$_3$CN, containing diprotonated [2.2.2]cryptand, crystallizes as a ladderlike 1D polymer, while NH$_4$]$_6$[Ni(H$_2$O)$_6$]$_2$[(UO$_2$)$_4$(1,2-PDA)$_6$]$_2$[(UO$_2$)$_4$(1,2-PDA)$_5$(H$_2$O)$_4$] (6) contains both a heavily corrugated 1D subunit and a discrete, tetranuclear anionic complex. The three complexes [Cu(bipy)$_2$(NO$_3$)][UO$_2$(1,2-PDA)(NO$_3$)] (7), [Ag(bipy)$_2$][UO$_2$(1,2-PDA)(NO$_3$)] (8), and [Ag(bipy)$_2$][UO$_2$(1,4-PDA)(NO$_3$)] (9) display 1D arrangements close to those in complexes 1-4 due to the presence of terminal nitrate ligands. The heterometallic complex [UO$_2$Pb(1,3-PDA)$_2$(phen)] (10) crystallizes as a diperiodic (2D) network built from 1D ribbons arranged in roof-tile fashion and connected to one another by Pb-O(oxo) links. [(UO$_2$)$_2$Pb$_2$(1,4-PDA)$_3$(HCOO)$_2$(phen)$_2$] (11) displays 1D triple-stranded (UO$_2$)$_2$(1,4-PDA)$_3$$^{2-}$subunits assembled into a corrugated 2D polymer by double rows of Pb(HCOO)(phen)$^+$ bridges. [Zn(bipy)$_3$][(UO$_2$)$_2$(1,2-PDA)(1,4-PDA)$_2$].H$_2$O (12) contains two phenylenediacetate isomers and displays zigzag chains linked to one another by dinuclear rings to give a 2D assembly containing large, elongated decanuclear rings. The two complexes [Cu(R,S-Me$_6$cyclam)][UO$_2$(1,3-PDA)(NO$_3$)]$_2$ (13) and [Ni(cyclam)][(UO2)$_2$(1,3-PDA)$_3$] (14), where cyclam = 1,4,8,11-tetraazacyclotetradecane and R,S-Me$_6$cyclam = 7(R),14(S)-5,5,7,12,12,14-hexamethylcyclam, are a 1D polymer analogous to 7-9 and a 2D species containing triple-stranded subunits similar to those in 11, respectively. These and previous results show that the phenylenediacetate ligands have a strong propensity to give 1D polymers with uranyl ion, which can only be partially overcome through the incorporation of additional metal cations, either bound to N-donors to form bulky, structure-directing counterions, or part of heterometallic polymers.
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Pierre Thuéry, Youssef Atoini, Jack Harrowfield. 1,2-, 1,3- and 1,4-Phenylenediacetate Complexes of Uranyl Ion with Additional Metal Cations and/or Ancillary N-Donor Ligands: Confronting Ligand Geometrical Proclivities. Crystal Growth and Design, American Chemical Society, In press, 19, pp.6611-6626. ⟨10.1021/acs.cgd.9b01032⟩. ⟨cea-02292579⟩

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