Abstract
Reactions of a tripodal ligand, N,N',N″-tris(3-pyridinyl)phosphoric triamide (TPPA), and a series of transition-metal ions result in the assembly of five discrete M(6)L(8) coordination cages [M(6)(TPPA)(8)(H(2)O)(12)](ClO(4))(12)·57H(2)O [M = Ni(2+) (1), Co(2+) (2), Zn(2+) (3), Cd(2+) (4)] and [Pd(6)(TPPA)(8)]Cl(12)·22H(2)O (5). X-ray structural analyses reveal that the cages have large internal cavities and flexible windows. The flexible ligand TPPA adopts the syn conformation in cages 1-4, but it transforms to the anti conformation in cage 5. Because of the conformational transformation, the sizes of the windows and the volume of the internal cavity of cage 5 are increased. (1)H NMR and electrospray mass spectrometric studies show that cage 5 maintains its structural integrity in solution. Additionally, compounds 3 and 4 exhibit strong blue fluorescent emissions, which are 1 order of magnitude higher than that of the free ligand.
Published Version
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