Synthesis and properties of Zn²⁺/Cd²⁺-directed self-assembled metallo-supramolecular polymers based on 1,4-diketo-pyrrolo[3,4-c]pyrrole (DPP) derivatives

Abstract

New building blocks based on 1,4-diketopyrrolo [3,4-c]pyrrole (DPP), 2,5-bis(2-ethylhexyl)-3,6-bis(5-[p-(2,2':6 0 ,2 00 -terpyridine-4 0 -yl) phenyl]thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M1) and 2,5bis(2-ethylhexyl)-3,6-bis(4-[p-(2,2 0 :6 0 ,2 00 -terpyridine-4 0 -yl) phenyl]phenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M2) were synthesized by the Suzuki Pd-catalyzed cross-coupling reaction. Under moderate conditions, directed self-assembly polymerizations by the transition metal ions Zn 2+ and Cd 2+ , respectively, were carried out. The metallo-supramolecular polymers P1Zn, P1Cd, P2Zn and P2Cd were obtained and fully characterized. The supramolecular polymers P2Zn and P2Cd, containing DPP modified by a phenyl unit, showed absorption maxima at about 504 and 506 nm in films. In contrast, the polymers P1Zn and P1Cd, in which the thiophene moiety-modified DPP was introduced, exhibited strong and broad visible absorption over 300-800 nm with maxima at about 601 and 598 nm and shoulder peaks at about 665 and 671 nm, respectively. The low band gaps estimated from CV of 1.52, 1.51, 1.58 and 1.58 eV for P1Zn, P1Cd, P2Zn and P2Cd, respectively, are also reported. Fig. 3 Cyclic voltammograms of supramolecular films recorded in CH 2 Cl 2 /0.1 M tetrabutylammonium hexafluorophosphate (TBAHFP) electrolyte at a scan rate of 100 mV s À1 .This journal is

Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films

“…PhDPP, TDPP, and palladium octabutoxy­phthalocyanine (PdPc) were synthesized and purified according to reported literature procedures. , PhTDPP was synthesized from 3,6-bis­(5-bromo­thien-2-yl)-2,5-bis­(2-ethyl­hexyl)-DPP as described below. Phenylboronic acid was purchased from Sigma-Aldrich.…”

Synthesis of the diketopyrrolopyrrole/terpyridine substituted carbazole derivative based polythiophenes for photovoltaic cells

“…Superior PV properties are generally expected for solar cells based on such metallosupramolecular polymers. 48 Conjugated polymers containing Fig. 7 The TEM images of PDPCz21/PC 71 BM blend solid films after annealing at 100 C for 10 min.…”

“…For example, Qiu et al reported an asymmetric thiophene/pyridine-anked DPP polymer (PyTDPP) that exhibited a narrow band gap, a wide light absorption range, and a relatively deep HOMO; PyTDPP-based PVCs displayed high PV efficiency. 47 Furthermore, Chen et al synthesized two terpyridine-functionalized DPP derivatives; 48 directed by zinc(II) and cadmium(II) ions, these DPP derivatives underwent polymerization to form metallo-supramolecular polymers, which exhibited low band gap energies (1.51-1.58 eV) and broad absorption bands (ranging from ca. 300 to 800 nm), suggesting potential applications in high-performance PV materials.…”

Modulating the Photophysical Properties and Electron Transfer Rates in Diketopyrrolopyrrole-Based Coordination Polymers

“…Another example of this strategy toward functional supramolecular materials has been reported by Chen and co-workers. In this work, the authors utilized a terpyridine-containing DPP derivative to generate supramolecular polymers through the coordination of Zn­(II) and Cd­(II) . Similar to the previous example, J-type aggregation was observed in these supramolecular materials, resulting in particular interesting chromophoric and physical properties.…”