Electronic and Crystal Structures of Nitrogen-Containing Electroconductive and Electroactive Polymers

Modeling the spectral properties of poly(x‐phenylenediamine) conducting polymers using a combined TD‐DFT and electrostatic embedding approach

“…[29][30][31][32] For poly-(p)-PDA there are some experimental reports indicating also the presence of a broad peak around 636 nm attributed to the occurrence of imine containing fragments. 29 Indeed, the presence of different fragments, including imine or diazo fragment for instance, 29 in variable relative ratio within each polymers chain cannot be excluded depending on experimental conditions such as solvent, acidity of the reaction environment, oxidizing agent and/or catalysts used for the synthesis. 32,33 Among the three polymeric chains, polym-PDA seems to be the most prone to branching and stitching during the polymerization thereby increasing the variety of chain fragments possibly present in the chain.…”

“…Simulated UV–Vis absorption spectra (solid curve) of PDA oligomers and experimental absorption band positions (blue dashed line) of poly‐( o,m,p )‐PDA 29–31 …”

“…Overall, the available experimental UV–Vis spectra of poly‐PDA polymers all exhibit two strong absorption bands located the first at 270, 276 and 290 nm and the second at 462, 459, and 405 nm for (poly‐( o )‐PDA), (poly‐( m )‐PDA) and (poly‐( p )‐PDA), respectively. The higher energy band has been experimentally attributed to π‐π* transitions localized on the aminobenzoic fragments while the latter is ascribed to the presence of phenazine fragments within the chains 29–32 . For poly‐( p )‐PDA there are some experimental reports indicating also the presence of a broad peak around 636 nm attributed to the occurrence of imine containing fragments 29 .…”

“…The higher energy band has been experimentally attributed to π‐π* transitions localized on the aminobenzoic fragments while the latter is ascribed to the presence of phenazine fragments within the chains 29–32 . For poly‐( p )‐PDA there are some experimental reports indicating also the presence of a broad peak around 636 nm attributed to the occurrence of imine containing fragments 29 . Indeed, the presence of different fragments, including imine or diazo fragment for instance, 29 in variable relative ratio within each polymers chain cannot be excluded depending on experimental conditions such as solvent, acidity of the reaction environment, oxidizing agent and/or catalysts used for the synthesis 32,33 .…”