Chiral Discrete and Polymeric Uranyl Ion Complexes with (1 R,3 S)-(+)-Camphorate Ligands: Counterion-Dependent Formation of a Hexanuclear Cage.

Reaction of (1 R,3 S)-(+)-camphoric acid (H2cam) with uranyl ions under solvo-hydrothermal conditions and in the presence of bulky countercations gave five chiral complexes of varying dimensionality. [Cu( R,S-Me6cyclam)][UO2(Hcam)2(HCOO)2] (1) and [Ni( R,S-Me6cyclam)][UO2(cam)(HCOO)2] (2), in which the formate coligand is formed in situ, involve very similar countercations, but 1 is a discrete, mononuclear complex, whereas 2 crystallizes as a one-dimensional (1D) coordination polymer, and NH-bond donation by the macrocyclic ligand of the countercation complexes is present in both. [Co(en)3][(UO2)4(cam)( R,R-tart)2(OH)]·3H2O (3), in which en is ethylenediamine and H4 R,R-tart is R,R-tartaric acid, contains three enantiomerically pure chiral species, and it displays a two-dimensional (2D) arrangement, with the countercation again involved in NH-bond donation. While [PPh4][UO2(cam)(NO3)] (4) is a 1D polymer, [PPh3Me]3[NH4]3[(UO2)6(cam)9] (5) is a discrete, homochiral, and homoleptic hexanuclear cage with C3 point symmetry and a trigonal prismatic arrangement of the uranium atoms. This cage differs from the octanuclear, pseudocubic uranyl camphorate species previously described, thus providing an example of modulation of the cage size through variation of the structure-directing counterions. The cage in 5 is closely associated with three PPh3Me+ cations, two of them outside and with their methyl group directed toward the prism basis center, and one inside the cage cavity. While complex 5 is nonluminescent, complexes 1 and 4 have emission spectra in the solid state typical of equatorially hexacoordinated uranyl complexes. Solid-state photoluminescence quantum yields of 2 and 23% have been measured for complexes 1 and 4, respectively.