Electroactive films of poly(tetraphenylporphyrins) with reduced bandgap

Selective anodic preparation of 1D or 2D electroactive deposits from 5,15-bis-(9H-fluoren-2-yl)-10,20-diphenyl porphyrins

“…2 and reported in Table 1, the E 4 ox values are highly anodic and in the case of H 2 DFDPP more anodic than the limit reached along the cyclic voltammetry. Compared with the fluorenyl unit oxidation in H 2 TFP (1.5 V) [20] and to the phenyl unit oxidation in H 2 TPP (>2.0 V) [21] and ZnTPP (>1.95 V) [21], E 3 ox should correspond to the fluorenyl units oxidation and E 4 ox to the phenyl units oxidation in H 2 DFDPP and ZnDFDPP. Fig.…”

“…In this case, the porphyrin macrocycles are linked by diaryl bridges and the electrochemical properties of the polymer depend on the nature of the electroactive aromatic unit (dithiophene [12], hydroxyphenyl [13], 3-methoxy-4-hydroxyphenyl [14], aminophenyl [13a,15], pcyclophanyl [16], 4-sulfonatophenyl [17] and other aryl groups [13a,18]). We previously described the anodic electrodeposition of porphyrins substituted by four 2-spirobifluorenyl units (free H 2 TSBFP or metallated M-TSBFP) [19], four 2-fluorenyl units (free H 2 TFP or metallated RuCOTFP) [20] or four phenyl units (free H 2 TPP or ZnTPP) [21] (see Scheme 2). In fact, poly(TSBFP)s are 3D materials that can be scratched off the electrode surface and have been used as efficient heterogeneous catalysts [19].…”

“…Poly(TPP)s are obtained at relatively high potential due to the fact that phenyl unit oxidation is more difficult than the fluorenyl or spirobifluorenyl one. Even so, the 2D poly(TPP) derivatives are very low bandgap polymers with bandgap values depending on the nature of the porphyrin [21]. Finally, only few groups results [22][23][24][25] showed polymerizations leading to porphyrins incorporated in a 1D wires (Scheme 1C).…”

Structure–property relationship of 4-substituted-spirobifluorenes as hosts for phosphorescent organic light emitting diodes: an overview

“…6,7 From a more fundamental point of view, the orthogonal configuration induced by the spiro carbon also allows to design shape persistent molecules with specific arrangements, which in turn has peculiar electronic consequences. 3,4,[8][9][10][11][12][13][14][15] In addition, the application field of the SBF scaffold is not only restricted to electronics and SBF has also found many other appealing applications as chiral ligand, [16][17][18][19] electropolymerizable building block, [20][21][22][23][24][25][26] homogeneous 27 and heterogeneous 23-25, 28, 29 catalysts or as building unit in coordination polymers, [30][31][32] clearly showing the versatility of this fragment. Sixteen positions of substitutions are available on the SBF backbone, eight on each fluorene unit (figure 1).…”

Synthesis and Optical Study of a New Oligophenylene

“…In fact, the modification of the monomer repeat unit or the attachment of functional groups onto the polymer backbone in a post-polymerization step can be used to achieve molecular level control of the structure and the properties of the polymer. Thus, it will be possible to (a) enhance the delocalization of electrons through the -conjugation on the polymer, (b) improve the optical and electrical properties, (c) give new functionalities to the polymer, and (d) reduce the polymer's band gap by the control of the HOMO-LUMO energy level [4][5][6][7][8][9][10][11][12][13][14][15].…”