High Solid State Photoluminescence Quantum Yields and Effective Color Tuning in Polyvinylpyridine Based Zinc(II) Metallopolymers

Abstract

Two series of amorphous metallopolymers are produced by grafting N′-substituted aroylhydrazide zinc(II) coordinated fragments onto poly-(4-vinylpyridine) at several concentrations. The polymers are characterized concerning their thermal behavior and absorption/emission properties. In the solid state their photoluminescence (PL) performances are remarkable. The emission color can be effectively tuned across the entire visible spectrum by varying the strength of the electron acceptor substituent on the tridentate ligand. As concerns the emission intensity, PL quantum yields measured on spin coated thin fi lms range from medium to high values and greatly exceed those of the model molecular complexes. Some of these values can be considered among the highest reported in the literature for metallopolymers. through chemical synthesis. [1][2][3][4][5][6][7][8] Among these materials polymers containing transition metal complexes (metallopolymers) are an important class whose electron rich ligands and metal centers can enhance optical and electronic properties. [9][10][11][12][13] In the last years our research group focused interest [14][15][16] on O,N ligands with functional substituents able to coordinate a d 10 transition metal ion like Zn(II) into stable chelate complexes with interesting photoluminescence performances. [ 17 ] In a recent study [ 15,16 ] N′-substituted aroylhydrazide fragments acted as O,N,O tridentate ligands in mono and dinuclear Zn(II) complexes with high photoluminescence quantum yield (PLQY) in the solid state. The ability of pyridine molecules to complete the coordination sphere of the complexes in penta or hexacoordinated arrangements was explored and its dominant contribution to the lowest unoccupied molecular orbital (LUMO) involved in the electronic transitions was pointed up. The present work has the purpose

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