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Optimizing Photoluminescence Quantum Yields in Uranyl Dicarboxylate Complexes: Further Investigations of 2,5-, 2,6-and 3,5-Pyridinedicarboxylates and 2,3-Pyrazinedicarboxylate/fr

Abstract : The 2,5-, 2,6-, and 3,5-pyridinedicarboxylic (2,5-, 2,6-and 3,5-pydcH$_2$), and 2,3-pyrazinedicarboxylic (2,3-pyzdcH$_2$) acids have been used to synthesize six uranyl ion complexes including various counterions under solvo-hydrothermal conditions. While [NH$_4$]$_2$[UO$_2$(2,6-pydc)$_2$]$\cdot$3H$_2$O (1) is a discrete, mononuclear species, [UO$_2$(2,6-pydc)$_2$Cu(R,S-Me6cyclam)] (2) crystallizes as a monoperiodic coordination polymer through axial bonding of copper(II) to carboxylate donors. [PPh$_3$Me][UO$_2$(OH)(2,5-pydc)]$\cdot$H$_2$O (3) and [Ni(R,S-Me6cyclam)][UO$_2$(OH)(2,5-pydc)]$_2$$\cdot$2H$_2$O (4) contain di-hydroxo-bridged dinuclear uranyl subunits assembled into homometallic, monoperiodic polymers. [(UO$_2$)2(3,5-pydc)$_2$(HCOO)$_2$Ni(R,S-Me6cyclam)] (5) crystallizes as a heterometallic diperiodic network with the V$_2$O$_5$ topology, and [PPh$_4$][UO$_2$(OH)(2,3-pyzdc)] (6) is a diperiodic species with sql topology. All complexes have well-resolved uranyl emission spectra in the solid state, and three of them have photoluminescence quantum yields among the highest reported for uranyl carboxylate complexes, 44% for 1, 71% for 3, and 36% for 6. 2
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Pierre Thuéry, Youssef Atoini, Sotaro Kusumoto, Shinya Hayami, Yang Kim, et al.. Optimizing Photoluminescence Quantum Yields in Uranyl Dicarboxylate Complexes: Further Investigations of 2,5-, 2,6-and 3,5-Pyridinedicarboxylates and 2,3-Pyrazinedicarboxylate/fr. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, In press. ⟨cea-02958532⟩

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