zn(ii)-phthalocyanine and zinc-tetraphenylporphyrin

Polymeric polyurethane nanofabrics doped by zinc tetraphenylporphyrin (ZnTPP) and/or zinc phthalocyanine (ZnPc) photosensitizers were prepared by the electrospinning method and characterized by microscopic methods, steady-state and time-resolved fluorescence, and absorption spectroscopy. Nanofabrics doped by both ZnTPP and ZnPc efficiently harvest visible light to generate triplet states and singlet oxygen O2(1Delta(g)) with a lifetime of about 15 micros in air atmosphere. The energy transfer between the excited singlet states of ZnTPP and ground states of ZnPc is described in details. All nanofabrics have bactericidal surfaces and photooxidize inorganic and organic substrates. ZnTPP and ZnPc in the polyurethane nanofabrics are less photostable than incorporated free-base tetraphenylporphyrin (TPP).

Topics: Indoles; Isoindoles; Metalloporphyrins; Molecular Structure; Nanostructures; Organometallic Compounds; Oxidation-Reduction; Oxygen; Particle Size; Photochemistry; Photosensitizing Agents; Polyurethanes; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Surface Properties; Time Factors; Zinc Compounds

Two-component adlayers consisting of zinc(II) phthalocyanine (ZnPc) and a metalloporphyrin, such as zinc(II) octaethylporphyrin (ZnOEP) or zinc(II) tetraphenylporphyrin (ZnTPP), were prepared by immersing either an Au(111) or Au(100) substrate in a benzene solution containing those molecules. The bimolecular adlayers thus prepared were investigated in 0.1 M HClO4 by cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM). A supramolecularly organized "chessboard" structure was formed for the ZnPc and ZnOEP bimolecular array on Au(111), while characteristic nanohexagons were found in the ZnTPP and ZnOEP bimolecular adlayer. EC-STM revealed that the surface mobility and the molecular re-organization of ZnPc and ZnOEP on Au(111) were tunable by manipulating the electrode potential, whereas the ZnTPP and ZnOEP bimolecular array was independent of the electrode potential. A "bottom-up" hybrid assembly of fullerene molecules was formed successfully on an alternate array of bimolecular ZnPc and ZnOEP molecules. The bimolecular "chessboard" served as a template to form the supramolecular assembly of C60 by selective trapping in the open spaces. A supramolecular organization of ZnPc and ZnOEP was also found on the reconstructed Au(100)-(hex) surface. A highly ordered, compositionally disordered but alternate array of ZnPc and ZnOEP was formed on the reconstructed Au(100)-(hex) surface, indicating that the bimolecular adlayer structure is dependent on the atomic arrangement of underlying Au in the formation of supramolecular nanostructures composed of those molecules. On the bimolecular array consisting of ZnPc and ZnOEP on the Au(100)-(hex), no highly ordered supramolecular assembly of C60 was found, suggesting that the supramolecular assembly of C60 molecules is strongly dependent upon the bimolecular packing arrangement of ZnPc and ZnOEP.

Topics: Electrodes; Fullerenes; Gold; Indoles; Isoindoles; Metalloporphyrins; Microscopy, Scanning Tunneling; Nanoparticles; Nanotechnology; Organometallic Compounds; Zinc Compounds