Transition Metal Titanophosphates with Intercalated Molecular Photoluminescence and Catalytic Properties.

In this study, α-TiP layered structure incorporating a heterometal center for organic ligand binding to enhance structural complexity and functionality were prepared. The protons of the α-TiP layer were replaced with zinc ions coordinated by 4-pyridinecarboxylic acid (PCA) and water to form a layer structure, TiZn(PO4 )2 (H2 O)(PCA) (1). The tetrahedral zinc center with coordinated water in 1 is unprecedented in zincophosphate or zinc-MOF systems and is usually only found in metalloenzyme systems. The neutral zincotitanophosphate layers, tightly stacked through hydrogen bonds, showed velcro-like behavior on intercalating 4,4'-trimethylenedipyridine (TMDP) reversibly. It rendered a remarkable luminescence property to 1, emitting blue-to-white light under UV excitation. Surprisingly, the replacement of TMDP for PCA in the hydrothermal synthesis still resulted in 1, plus another structure, Ti4 Zn2 (H2 TPB)(PO4 )4 (HPO4 )4 (H2 PO4 )2 (2) (TPB=1,2,4,5-tetra(4-pyridyl)benzene). Clearly, in situ C-C cracking and C-C coupling of TMDP simultaneously occurred to generate PCA and TPB and thereafter the oxidant, Zn(NO3 )2 , was quantitatively determined to isolate crystal 1 from 2. The structure of 2 also featured α-TiP layers with pedant Zn tetrahedra but formed a three-dimensional neutral framework through TPB. For the first time, α-TiP-derived structures and their properties have been elucidated, which help in understanding intriguing in situ ligand formation and intercalation-induced luminescence, to exploit potential photocatalysis in polymerization.