Uranyl ion coordination polymers with the dibenzobarrelene-based rac- and (R,R)-trans-9,10-dihydro-9,10-ethanoanthracene-11,1 2-dicarboxylate ligands

trans-9,10-Dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (deadcH2), in its racemic or R,R enantiomeric forms, has been used to synthesize eight uranyl ion complexes under solvo-hydrothermal conditions. [UO2(deadc)].1.5CH(3)CN (1) and [H2NMe2](2)[(UO2)(2)(deadc)3].2H(2)O (2) crystallize as monoperiodic coordination polymers in which deadc2- forms both 4- and 7-membered chelate rings. Although synthesized in the same conditions as 2, the enantiomerically pure complex [H2NMe2](4)[(UO2)(2)(O)(R,R-deadc)2]2 (3) is a discrete tetranuclear complex containing two mu 3-oxo anions. Association with the zwitterion Ni(tpyc)2, where tpyc- is 2,2' :6' ,2'' -terpyridine-4' -carboxylate, gives [(UO2)(2)(deadc)(deadcH)(NO3)Ni(tpyc)2].CH3CN.2H(2)O (4), a rake-shaped monoperiodic assembly. [UO2(deadc)(DMA)] (5), [UO2(deadc)] (6) and [PPh4](2)[(UO2)(2)(R,R-deadc)3] (7) crystallize as diperiodic networks with the fes, sql and hcb topologies, respectively, the thick layers formed being coated on both sides by protruding, hydrophobic dibenzobarrelene groups. Finally, [(UO2)2Ag(2)(deadc)(3)(CH3CN)2].0.5H(2)O (8) contains monoperiodic uranyl-deadc2- subunits which are assembled into a triperiodic framework by bridging silver(i) cations, the latter interacting with both carboxylate groups and aromatic rings. Except for 6, all these complexes are emissive with photoluminescence quantum yields of 2-26%, and most spectra display the usual vibronic fine structure of uranyl emission.