New deeply coloured and fluorescent polymers with 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole units in the main chain

Abstract

SUMMARY: New deeply coloured and fluorescent copolyesters and -urethanes with 1,4-dioxo-3,6-diphenylpyrrolo [3,4-c]pyrrole (DPP) units in the main chain were prepared. The chromophoric units are incorporated in the backbone via their N-alkylated lactam groups. The DPP-containing monomer 1,4-dioxo-2,5-bis(6-hydroxyhexyl)-3,6-diphenylpyrrolo[3,4-c]pyrrole (2) was obtained by N-alkylation of 1,4-dioxo-3,6-diphenylpyrrolo [3,4-c]pyrrole (1) with 6-chlorohexanol. Copolyesters were prepared by (a) solution polycondensation of mixtures of 2 and 1,12-dodecanediol with terephthaloyl chloride and (b) melt polycondensation of the diol mixture with dimethyl terephthalate using tetrabutoxytitanium as catalyst. Copolyurethanes were prepared by polyaddition of mixtures of 2 and 1,12-dodecanediol with hexamethylene diisocyanate. The copolyesters are readily soluble in common organic solvents, while the copolyurethanes are only soluble in rather exotic solvents such as p-cresol. Polymer solutions are yellow to orange with optical absorption maximum at 470 nm and fluorescence maximum at 520 nm, the Stokes-shift being about 50 nm. All copolymers are partially crystalline, the crystallinity decreasing with increasing DPP content. Possible origins for the influence of the DPP content on the crystallinity of the polymers are discussed. The thermal stability of the copolyesters is independent of the DPP content, the decomposition temperature being about 646 K. The limit of thermal stability of the copolyurethanes is about 600 K and increases slightly with DPP content.

Electrochemical Polymerization of Bis(3,4‐ethylenedioxythiophene)‐Substituted 1,4‐Diketo‐3,6‐diphenyl‐pyrrolo[3,4‐c]pyrrole (DPP) Derivative

“…DPPs are insoluble in water or common organic solvents due to π‐π stacking and a strong hydrogen bonded structure in the solid state 3. Previous studies have shown that soluble DPP derivatives with deep color and strong luminescence can be prepared upon alkylation of the lactam units 4, 5. If properly functionalized, alkylated DPP monomers can be used for the preparation of oligomers,6 dendrimers,7 and polymers 8–13.…”

Red Emitting Diphenylpyrrolopyrrole (DPP)‐Based Polymers Prepared by Stille and Heck Coupling

“…[4] In order to use the DPP chromophore in electronic devices, it is therefore necessary to prepare soluble and film forming DPP compounds such as oligomers, [5] dendrimers, [6] and polymers. [7][8][9][10][11][12][13][14][15] These materials show intense red color, strong red photoluminescence, and electroluminescence, [12,14] which renders them attractive as active materials in a variety of electronic devices.…”

“…DPP-containing polymers have been prepared upon radical polymerization, [8,9] polycondensation, [10] polyaddition, [10] polymer modification, [13] and Pd-catalyzed cross-coupling reactions. [11,12,14,15] Especially, the latter approach allows for the preparation of a variety of new DPP-containing p-conjugated polymers.…”

Novel, soluble diphenyl-diketo-pyrrolopyrroles: Experimental and theoretical study

“…Furthermore, some of their physical properties such as high melting points are exceptional in view of their very low M r , in conventional pigment molecule terms. It has been shown that DPP units introduced into various materials, such as polymers [14][15][16][17][18][19][20][21][22][23] dendrimers [24], polymer-surfactant complexes [25], and oligomers [26] results in deeply coloured, highly photoluminescent [15][16][17][18][19][20][21][22][23][24][25][26] and electroluminescent [19,20] materials. Owing to their interesting properties, there is wide range of possible applications which have been already investigated covering for example latent pigment [27], charge generating materials for laser printers and information storage systems [28][29][30][31][32][33], solid-state dye lasers [30] or gas detectors [34,35].…”