Abstract
Two discrete M3L2 metal-organic architectures, 1 and 2, have been constructed by reaction of a newly designed tripodal tris-bidentate ligand L with M(NO3)2 (1: M=Zn; 2: M=Cd). Both complexes together with L have been structurally elucidated by single-crystal X-ray crystallography. Complex 1 exhibits a cationic M3L2 coordination architecture bearing three positive charges balanced by three uncoordinated nitrates, while 2 shows a neutral M3L2. 1 and 2 both adopt a compressed trigonal prism shape but show no internal cavity due to close ligand-to-ligand interactions. They display totally different intermolecular packing modes in the solid state, which strongly influence the intermolecular π–π interactions. Complex 1 has been arrayed such that each M3L2 is surrounded by three neighboring C 3-symmetry related ones, whereas 2 exhibits a columnar molecular stacking. The distinctive intermolecular packing modes in the solid state between 1 and 2 bring about a small but discernible red shift (4 nm) corresponding to the π–π ∗ electronic absorption.
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