title: Fabrication and optical nonlinearities of composite films derived from the water-soluble Keplerate-type polyoxometalate and chloroform-soluble porphyrin.
abstract: Composite films derived from the water-soluble Keplerate-type polyoxometalate (NH4)42[Mo132O372(CH3COO)30(H2O)72]·ca. 300H2O·ca. 10CH3COONH4 (denoted (NH4)42{Mo132}) and chloroform-soluble tetraphenylporphyrin perchlorate [H2TPP](ClO4)2 are successfully fabricated by a layer-by-layer self-assembly method and characterized by UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS). The structure of the {Mo132} and [H2TPP](2+) in the films remain intact in light of the results of UV-vis spectroscopy and XPS. UV-vis spectra measurements reveal that the amounts of deposition of {Mo132} and [H2TPP](2+) remain constant in every adsorption cycle in the composite films assembly process. Nonlinear optical properties of the composite films have been investigated by using the Z-scan technique at a wavelength of 532 nm and pulse width of 7 ns. The results show that the composite films have notable nonlinear saturated absorption and self-defocusing effects. The combination of {Mo132} with [H2TPP](2+) can result in composite films with remarkably enhanced optical nonlinearities. The interfacial charge transfer induced by laser from porphyrin to POM in the films is thought to play a key role in the enhancement of NLO response. The third-order NLO susceptibility χ((3)) of the composite films increases with the increase of film thickness.
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Institute of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. China. zhouys@mail.buct.edu.cn ljzhang@mail.buct.edu.cn.
authors.forename: Zonghai
authors.initials: Z
authors.lastname: Shi
authors.forename: Yunshan
authors.initials: Y
authors.lastname: Zhou
authors.forename: Lijuan
authors.initials: L
authors.lastname: Zhang
authors.forename: Di
authors.initials: D
authors.lastname: Yang
authors.forename: Cuncun
authors.initials: C
authors.lastname: Mu
authors.forename: Haizhou
authors.initials: H
authors.lastname: Ren
authors.forename: Farooq Khurum
authors.initials: FK
authors.lastname: Shehzad
authors.forename: Jiaqi
authors.initials: J
authors.lastname: Li