Copolymeric films obtained by electropolymerization of porphyrins and dipyridyl-spacers including Dawson-type polyoxometalates

Abstract

International audienc

Photocatalytic recovery of metals by Lindqvist-type polyoxometalate–porphyrin copolymer

“…UV-visible spectra of both copolymers on ITO electrodes presented similar characteristics [27]. They exhibit a large Soret absorption band (Figure 1A), which was red shifted by 15 and 20 nm compared to the ZnOEP and H 2 T 2 P monomer respectively [27].…”

“…The rms surface roughness of the film was 3.5 nm for 1 mm 2 area. For poly-V 6 O 13 -ZnOEP the diameter and the height of the coils were almost two times larger (Figures 1D and D ) [27].…”

“…The syntheses of the copolymers were achieved using our electropolymerization method, as reported earlier [25,26] [27].…”

“…Using this method, the poly-Py-V 6 O 13 -Py-H 2 T 2 P and the poly-Py-V 6 O 13 -Py-ZnOEP hybrid copolymers were prepared as described previously [27].…”

“…Note that the free base meso-5,15ditolylporphyrin (H 2 T 2 P) presents only two meso positions occupied by one substitutable proton at positions C10 and C20 while the zinc-βoctaethylporphyrin (ZnOEP) presents four substitutable meso positions at C5, C10, C15 and C20 (top of Scheme 1). The described electrochemical synthesis of the copolymers uses the previously reported E(EC N EC B ) n E process of nucleophilic substitution on porphyrins [17][18][19][26][27][28][29]. As soon as the iterative scans were performed at an anodic potential suffi- ciently high to allow the formation of the porphyrin dication, the formation of a copolymer coating the working electrode was observed.…”