Hybrid Assemblies And Spectroscopic Properties Of Luminescent Chromophores With Modified Layered Zirconium Phosphate

Hybrid assemblies of organic chromophores and inorganic compounds have been studied extensively to improve the spectroscopic performance of the chromophores. In this paper, the modified zirconium phosphate, in which the interval of the interlayer is adjustable, was chosen as framework of photon antenna. As luminescent chromophores, the metalloporphyrin compexes have been assembled successfully into the lamellar framework, and the optical property enhanced obviously. In addition, efficient energy transfer between fluorescein (F1) and rhodamine B(RhB) was observed in the framework.Two kinds of lamellar frameworks were prepared-octadecyltrimethylammonium zirconium phosphate (OTZrP) and dodecyltrimethylammomium zirconium phosphate (DTZrP). The suitable enlargement of the interlayer spacing for the framework is beneficial to the intercalation of complicated molecules; Four porphyrins complexes were synthesized- silver (II) tetra-phenyl porphyrin (TPP-Ag), zinc (II) tetra-phenyl porphyrin (TPP-Zn), silver (II) tetra-(p-methylphenyl) porphyrin (TMPP-Ag) and zinc(II) tetra-(p-methylphenyl) porphyrin (TMPP-Zn).These as-prepared porphyrin complexes were inserted into OTZrP, and obtained four compounds (TPP-Zn/OTZrP, TPP-Ag/OTZrP, TMPP-Zn/OTZrP and TMPP-Ag/OTZrP). The optical properties of metalloporphyrins assembled into OTZrP were optimized. Especially, the intensity of fluorescence was enhanced obviously. The similar results of TPP-Zn and TPP-Ag intercalated into DTZrP were also observed. It is concluded that OTZrP and DTZrP provide special microenvironment, which can improve the optical properties of metalloporphyrins.Energy transfer between F1 and RhB was observed in the OTZrP as framework. When the concentration of F1 was fixed and that of RhB was increased, the emission of F1 decreased gradually accompanying with gradual raise of that of RhB, which implies the efficient energy transfer from F1 to RhB. In aqueous solution, the phenomenon can not be observed. Therefore, OTZrP as framework can promote evident energy transfer between F1 and RhB.