Woven, Polycatenated, or Cage Structures: Effect of Modulation of Ligand Curvature in Heteroleptic Uranyl Ion...

Combining the flexible zwitterionic dicarboxylate 4,4'-bis(2-carboxylatoethyl)-4,4'-bipyridinium (L) and the anionic dicarboxylate ligands isophthalate (ipht^2-) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda^2-), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO₂)₂(L)(ipht)₂] (1) and [(UO₂)₂(L)(1,2-pda)₂]·2H₂O (2) have the same stoichiometry, and both crystallize as monoperiodic coordination polymers containing two uranyl-(anionic carboxylate) strands united by L linkers into a wide ribbon, all ligands being in the divergent conformation. Complex 3, [(UO₂)₂(L)(1,3-pda)₂]·0.5CH₃CN, with the same stoichiometry but ligands in a convergent conformation, is a discrete, binuclear species which is the first example of a heteroleptic uranyl carboxylate coordination cage. With all ligands in a divergent conformation, [(UO₂)₂(L)(1,4-pda)(1,4-pdaH)₂] (4) crystallizes as a sinuous and thread-like monoperiodic polymer; two families of chains run along different directions and are woven into diperiodic layers. Modification of the synthetic conditions leads to [(UO₂)₄(LH)₂(1,4-pda)₅]·H₂O·2CH₃CN (5), a monoperiodic polymer based on tetranuclear (UO₂)₄(1,4-pda)₄ rings; intrachain hydrogen bonding of the terminal LH⁺ ligands results in diperiodic network formation through parallel polycatenation involving the tetranuclear rings and the LH⁺ rods. Complexes 1-3 and 5 are emissive, with complex 2 having the highest photoluminescence quantum yield (19%), and their spectra show the maxima positions usual for tris-κ²O,O'-chelated uranyl cations.