A new family of organometallic/inorganic nanohybrid Langmuir−Blodgett (LB) films consisting of
rigid-rod organomercury acetylide complex (OMA-C16 or OMA-C8) as the π-conjugated organometallic
molecule, tungsto(molybdo)phosphoric heteropolyacids HPA (HPA = H3PMo12O40, H3PW12O40, H6P2Mo18O62, or H6As2W18O62) of the Keggin and Dawson structures as the inorganic component, and
octadecylamine (ODA) as the auxiliary film-forming agent were prepared and characterized by π−A
isotherms, UV−vis absorption spectra, fluorescence spectra, atomic force microscopy imaging, scanning
tunneling microscopy, surface photovoltage spectroscopy, and low-angle X-ray diffraction. Our
experimental results indicate that steady, even, and ordered Langmuir and LB films are formed in pure
water and heteropolyacid subphase. They typically have a highly organized lamellar structure in which
a monolayer of HPA is arranged alternately with well-ordered layers of OMA (and also ODA for OMA-C16) and the periodicity of the layered structure for the OMA-C16/ODA/H3PMo12O40 LB film is ca. 3.7
nm. Luminescence spectra of hybrid LB films show that HPA can quench the emission of OMA-C16 and
OMA-C8 to some extent. These LB composites show good photovoltage responses and a photovoltage
of 103 μV can be obtained for the OMA-C16/ODA/H3PMo12O40 system when it is excited by light at 330
nm. The monolayer LB films on silica wafer can also display interesting electrical conductivity behavior.
A new series of organometallic/inorganic hybrid Langmuir-Blodgett (LB) films containing an organometallic gold(i) aryleneethynylene metal complex (OMA) as the π-conjugated organometallic molecule and a polyoxometalate (POM, POM = H3BW12O40, H6As2W18O62, or H6P2Mo18O62) of the Keggin and Dawson structure as the inorganic composite, were prepared and characterized by π–A isotherms, UV-vis absorption spectra, photoluminescence spectra, atomic force microscopy imaging, scanning tunnelling microscopy, and surface photovoltage spectroscopy. Our experimental results indicate that stable, well defined and well organized Langmuir and LB films are formed in pure water and polyoxometalate subphases. There is a quenching effect in the luminescence of the gold(i) complex when it is made into the LB films. The OMA/POM hybrid LB films display strong photovoltage effect in the UV-vis region. The photovoltage response of OMA/H6As2W18O62 can be as high as 3338 μV. OMA/POM monolayer films show good electrical conductivity, and the tunnelling current for a OMA/H3BW12O40 monolayer film amounts to 50 to approximately –100 nA when the voltage is set at ±9 V.
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