Electrochemical Deposition of a Pyrrole-1-yl Substituted Perylene Diimide for Photoluminescence and Electrochromism

Abstract

tetracarboxylic acid dianhydride. PDI-2Py could be electrodeposited by scanning the potential between 0 and 1.2 V vs. Ag/Ag ϩ in a potentiodynamic mode to form a red film stably adhering to a glassy carbon or indium tin oxide electrodes which was insoluble in common organic solvents. Considering that PDI without pyrrole moiety could not be electrodeposited in the same potential range and that the pyrrole moiety can be electropolymerized at above ca. 0.9 V vs. Ag/Ag ϩ , we conclude that PDI-2Py was electropolymerized to form the corresponding polymer ͓P͑PDI-2Py͔͒. The resulting P͑PDI-2Py͒ exhibited photoluminescence ( max : 629 nm) upon photoexcitation at 573 nm. From the electrochromic study, P͑PDI-2Py͒ turned red ( max : 573 nm) and emerald ( max : 788 nm) at 0 and Ϫ1.8 V vs. Ag/Ag ϩ , respectively. P͑PDI-2Py͒ film formation by electrodeposition of PDI-2Py is one of the promising methods for multilayer fabrications because the insoluble characteristics of the resulting film in common organic solvents allows variety in the choice of solvents for the coating of an upper layer.

Multichromophoric electrochromic polymers: colour tuning of conjugated polymers through the side chain functionalization approach

“…Conjugated polymers incorporating rylene diimides [159][160][161][162][163][164] were also reported by several groups. As an example, Lee et al reported the synthesis and electrochemical deposition of a pyrrole monomer N-substituted with a perylene diimide unit (PDI).…”

“…As an example, Lee et al reported the synthesis and electrochemical deposition of a pyrrole monomer N-substituted with a perylene diimide unit (PDI). 159 The polymer was electrochemically prepared by the CV technique but, as an effect of the presence of the bulky PDI substituent judging from the current density around 0.25 V in monomer-free solution, the degree of polymerization was very low. The response times of the electrochromic film upon switching the potential from 0 V to 1.8 V vs. Ag/Ag + , corresponding to p(PDI-2Py) and p(PDI-2Py) 2À respectively, were 160 s and 190 s. This process was accompanied by a colour change of the film from red (l max : 573 nm) to emerald (l max : 788 nm) (Fig.…”

Polypyrrole derivatives for electrochromic applications

“…56 In another inspiring study, the electrochemical deposition of a pyrrole-1-yl substituted perylene diimide (11) was achieved. 57 Poly(11) turned from red (l max : 573 nm) to emerald (l max : 788 nm) upon oxidation. For poly (11) the time required for reaching 90% of the ultimate absorbance was calculated as 160 s. Such a slow response was attributed to the low conductivity of the polymer, which was considered to be because of the large separation of perylene diimide, as well as the insulating nature of the polypyrrole backbone in the operating potential range.…”

Formation of insoluble perylenetetracarboxylic diimide films by electro- or photo-crosslinking of pyrrole units

“…9 However, owing to the intrinsic poor solubility of PDI, fabrication of a PDI film with desired morphology and properties has been a challenging issue especially in construction of a device based on PDI. 11 In this communication, we report on the synthesis and unique film formation characteristics of PDI-4Py either by electropolymerization or by photo-crosslinking induced by simple visible light irradiation (> 500 nm) to form a very robust insoluble PDI film. The p-stacking effect can be reduced by introducing bulky groups into 1-, 6-, 7-, and 12positions or into N-positions of PDI.…”

“…1) containing two pyrrole units that can be electrochemically polymerized to form an insoluble PDI film. 11 In this communication, we report on the synthesis and unique film formation characteristics of PDI-4Py either by electropolymerization or by photo-crosslinking induced by simple visible light irradiation (> 500 nm) to form a very robust insoluble PDI film. To the best of our knowledge, this is the first example of oxidative photopolymerization of pyrrole derivatives sensitized by a purely organic sensitizer such as PDI.…”