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- 저자 : J. A. Causley (검색결과 1 건)
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Photoluminescence and photo-redox reactions of poly(2-methoxyaniline-5-sulfonic acid)
L.A.P. Kane-Maguire,Kane-Maguire,J. A. Causley,G. G. Wallace 한국물리학회 2004 Current Applied Physics Vol.4 No.2-4
The water-soluble fully sulfonated polyaniline, poly(2-methoxyaniline-5-sulfonic acid) has been found to photoluminesce in itsemeraldine oxidation state, ES(PMAS). Excitation of aqueous solutions at 450530 nm, near its characteristic absorption band at473 nm, led to emission at ca. 600 nm (2.1 eV). Calculations incorporating cyclic voltammetric data for ground state PMAS suggestthat the photo-generated ES.(PMAS) excited state should be both a very powerful oxidising agent and a strong reducing agent (ca.2.7 and 1.1 V of oxidising and reducing power, respectively). This prediction has been conrmed from photolysis studies ofES(PMAS) in the presence of the potentially reducible cobalt(III) cations CoCl(NH3)2þ5 , Co(H2O)(NH3)3þ5 and Co(en)3þ3 . In water,photo-oxidation of the ES(PMAS) to its fully oxidised pernigraniline base PB(PMAS) form was conrmed by UVvisible spec-troscopy. In the case ofK-Co(en)3þ3 as the acceptor, strong support for the concomitant reduction of the Co(III) complex to thecorresponding Co(II) species was obtained from its observed racemisation. Relatively low quantum eciencies (<3%) wereestablished for these novel, photo-initiated redox reactions. These photo-redox reactions were preceded by a photo-initiated con-formational change in the ES(PMAS) polymer from an ‘‘extended coil’’ to a ‘‘compact coil’’ conformation. The presence of addedNaþ and NHþ4 ions had a marked inuence on the nature of the photo-reactions, with Naþ ions retarding the photo-assistedelectron transfer, while NHþ4 ions prevented the initial conformational change in the ES(PMAS).
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