Hybrid hexagonal nanorods of metal nitride clusterfullerene and porphyrin using a supramolecular approach

Hexagonal nanorods of metal nitride clusterfullerene Sc(3)N@C(80) (I(h)) encapsulated in zinc meso-tetra(4-pyridyl) porphyrin (ZnTPyP) (Sc(3)N@C(80)-ZnTPyP nanorods) are prepared for the first time using a supramolecular approach. By introducing water as the solvent of cetyltrimethylammonium bromide (CTAB) surfactant, the effects of the solvent and the ratio of the reactants have been studied so as to control the length and size distribution of the Sc(3)N@C(80)-ZnTPyP nanorods. The encapsulation nature and hybrid structures of Sc(3)N@C(80)-ZnTPyP nanorods are confirmed by TEM, EDX, TGA and Raman spectroscopies. XRD study on the internal structure of Sc(3)N@C(80)-ZnTPyP nanorods suggests that ZnTPyP molecules tend to self-assemble in the axial direction. The UV-vis electronic absorption spectrum of Sc(3)N@C(80)-ZnTPyP nanorods shows broader and stronger absorptions in the visible region than those of the components Sc(3)N@C(80) and ZnTPyP. The comparison of the UV-vis electronic absorption spectra of Sc(3)N@C(80)-ZnTPyP and C(60)-ZnTPyP nanorods reveals the influence of the electronic structures of fullerenes on the aggregative interactions between fullerene and ZnTPyP. The fluorescence emission intensity of Sc(3)N@C(80)-ZnTPyP nanorods exhibits a strong quenching (similar to 88%) compared to the pure ZnTPyP nanotubes, suggesting that photo-induced electron transfer from the excited ZnTPyP to Sc(3)N@C(80) might occur. An electrochemical study of Sc(3)N@C(80)-ZnTPyP nanorods in comparison with those of ZnTPyP and Sc(3)N@C(80) corroborate the hybrid nature of Sc(3)N@C(80)-ZnTPyP nanorods and reveal the interactions between Sc(3)N@C(80) and ZnTPyP molecules.