photooxidation of some metallocenes in a polymer matrix光致氧化的茂金属聚合物基质.pdfVIP

Molecules 2005, 10, 708-727 molecules ISSN 1420-3049 Photooxidation of Some Metallocenes in a Polymer Matrix Biswanath Mallik Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata-700 032, India. Tel. (+91)-33-2473 4971 Ext. 255, Fax (+91)- 33-2473 2805, e-mail: spbm@mahendra.iacs.res.in Received: 3 December 2004 / Accepted: 5 January 2005 / Published: 14 July 2005 Abstract: The changes in the electronic absorption spectra (UV-Vis) of some metallocene-doped poly(methyl methacrylate) (PMMA) thin films containing chloroform molecules as impurities were studied after photoexcitation in the nitrogen atmosphere. Photoexcitations were made by monochromatic radiation (using a Xe-lamp source and a monochromator) at an interval of few nanometers in the spectral range 210-750 nm. The changes in spectra were studied as a function of photoexcitation time (duration), amount of metallocene in the film and the amount of chloroform molecules present in the film. Occurrence of photoinduced charge-transfer between some metallocenes and chloroform molecules confined in the PMMA thin films was observed, which indicated photooxidation of the metallocenes in the polymer matrix. Photoresponse in the case of ferrocene derivatives was observed to decrease with the increase in the value of para- Hammett constant for the substituent attached to the ferrocene unit and also with increasing half-wave