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 (H 2 O)](ClO 4 ) 2 ( 1 ), [Zn 4 (tib) 2 (PBDA) 3 (OH) 2 ]·4H 2 O ( 2 ), [Zn(tib)(HPBDA)]ClO 4 ( 3 ), [Zn 2 (tib)(PBDA)Cl 2 ]·2H 2 O ( 4 ), [Zn 4 (tib) 2 (PBDA) 3 Cl 2 ] ( 5 ), [Zn 2 (tib) 2 (PBDA)](NO 3 ) 2 ·2H 2 O ( 6 ), and [Zn 2 (tib)(PBDA)I 2 ]·2H 2 O ( 7 ) [tib = 1,3,5-tris(1-imidazolyl)benzene, H 2 PBDA = 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.