Interpenetrating and Self-Penetrating Zinc(II) Complexes with Rigid Tripodal Imidazole-Containing Ligand and Benzenedicarboxylate

Seven new Zn(II) metal−organic frameworks [Zn(tib)2(H2O)](ClO4)2 (1), [Zn4(tib)2(PBDA)3(OH)2]·4H2O (2), [Zn(tib)(HPBDA)]ClO4 (3), [Zn2(tib)(PBDA)Cl2]·2H2O (4), [Zn4(tib)2(PBDA)3Cl2] (5), [Zn2(tib)2(PBDA)](NO3)2·2H2O (6), and [Zn2(tib)(PBDA)I2]·2H2O (7) [tib = 1,3,5-tris(1-imidazolyl)benzene, H2PBDA = p-benzenedicarboxylic acid] have been prepared and characterized by elemental, IR, thermogravimetric and X-ray diffraction analyses. Complexes 1 and 4 are two-dimensional (2D) networks with different topologies, which are further linked together to three-dimensional (3D) frameworks by hydrogen bonds. For 3, partial deprotonated HPBDA− is terminally coordinating to Zn(II) to form a 2D network. Complexes 2, 5, and 7 are 2-fold interpenetrated 3D frameworks, while 6 has a self-penetrating 3D structure. The influences of reaction temperature and counteranion on the structures of the complexes are discussed. The photoluminescence and nonlinear optical properties are investigated.