Search Results (8)

Carbazole derivatives, carbazole-containing polymers and iridium complexes are of interest due to many possible applications in photonics, electronics and biology, particularly as active or hole-transporting layers in organic as well as perovskite devices due to their interesting properties. Here, a series of carbazole-fluorene conjugated copolymers with various substituents at the N-carbazole position (2-methoxycarbonylethyl, 2-carboxyethyl, 2-ethylhexyl, and nonan-2,4-dionatoiridium(III)bis(2-phenylpyridine-N,C^2′)-9-yl) was prepared by Suzuki coupling. Their photophysical, electrochemical and electroluminescence (EL) properties were studied. Effects of molecular weight and substituents attached to carbazole unit on their properties are reported. The carbazole-fluorene copolymers in dilute solutions exhibited intense photoluminescence (PL) emission in the blue spectral region with high PL quantum yields (78–87%) except for the copolymer with the iridium complex (23%). Similar PL spectra were observed in dilute solutions. More pronounced differences were found in thin film PL and EL properties due to excimer/aggregate formation. Light-emitting devices (LEDs) made of copolymers with 2-ethylhexyl as N-carbazole substituent exhibited efficient EL emission with the best performance and the lowest EL onset voltages (3–4 V), while the LEDs made of copolymers with other substituents were not as efficient, but showed anomalous behavior and memory effects in current-voltage characteristics promising also for bio-inspired electronics. Full article

Donor-acceptor (D-A) copolymers containing perylene-3,4,9,10-tetracarboxydiimide (PDI) electron-acceptor (A) units belonging to n-type semiconductors are of interest due to their many potential applications in photonics, particularly for electron-transporting layers in all-polymeric or perovskite solar cells. Combining D-A copolymers and silver nanoparticles (Ag-NPs) can further improve material properties and device performances. Hybrid layers of D-A copolymers containing PDI units and different electron-donor (D) units (9-(2-ethylhexyl)carbazole or 9,9-dioctylfluorene) with Ag-NPs were prepared electrochemically during the reduction of pristine copolymer layers. The formation of hybrid layers with Ag-NP coverage was monitored by in-situ measurement of absorption spectra. The Ag-NP coverage of up to 41% was higher in hybrid layers made of copolymer with 9-(2-ethylhexyl)carbazole D units than in those made of copolymer with 9,9-dioctylfluorene D units. The pristine and hybrid copolymer layers were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy, which proved the formation of hybrid layers with stable Ag-NPs in the metallic state with average diameters <70 nm. The influence of D units on Ag-NP diameters and coverage was revealed. Full article

A 1,4-bis((9H-carbazol-9-yl)methyl)benzene (DCB)-containing homopolymer (P(DCB)) and four DCB- and ED-derivative (3,4-ethylenedioxythiophene (EDOT) and 3,4-ethylenedioxythiophene-methanol (EDm))-containing copolymers (P(DCB-co-ED), P(2DCB-co-ED), P(DCB-co-EDm), and P(2DCB-co-EDm)) were electropolymerized on ITO-polyethylene terephthalate (PET) substrates and their electrochromic performances were studied. DCB displays a lower E_onset than that of EDOT and EDm, conjecturing that the biscarbazole-containing DCB group shows a stronger electron-donating property than that of the ED derivatives. The P(2DCB-co-ED) film presents slate grey, dark khaki, and dark olive green at 0.0, 1.0, and 1.2 V. Bleaching-to-coloring switching studies of polymers show that P(2DCB-co-EDm) shows a high ΔT (31.0% at 725 nm) in solutions. Five dual-layer flexible electrochromic devices (ECDs) based on P(DCB), P(DCB-co-ED), P(2DCB-co-ED), P(DCB-co-EDm), and P(2DCB-co-EDm) as the anodic materials and PEDOT-PSS as the cathodic material are constructed. The P(2DCB-co-ED)/PEDOT-PSS flexible ECD shows a high ΔT (40.3% at 690 nm) and long-term electrochemical cycling stability, while the P(DCB-co-EDm)/PEDOT-PSS ECD shows a high ΔT (39.1% at 640 nm) and short response time (≤1.5 s). These findings offer us a new structural insight for the valuable design of conjugated polymers in high-contrast, flexible ECDs. Full article

Herein, we report the Suzuki–Miyaura catalyst-transfer polycondensation (SCTP) of triolborate-type carbazole monomers, i.e., potassium 3-(6-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl)triolborate (M1) and potassium 2-(7-bromo-9-(2-octyldodecyl)-9H-carbazole-2-yl) triolborate (M2), as an efficient and versatile approach for precisely synthesizing poly[9-(2-octyldodecyl)-3,6-carbazole] (3,6-PCz) and poly[9-(2-octyldodecyl)-2,7-carbazole] (2,7-PCz), respectively. The SCTP of triolborate-type carbazole monomers was performed in a mixture of THF/H₂O using an initiating system consisted of 4-iodobenzyl alcohol, Pd₂(dba)₃•CHCl₃, and t-Bu₃P. In the SCTP of M1, cyclic by-product formation was confirmed, as reported for the corresponding pinacolboronate-type monomer. By optimizing the reaction temperature and reaction time, we successfully synthesized linear end-functionalized 3,6-PCz for the first time. The SCTP of M2 proceeded with almost no side reaction, yielding 2,7-PCz with a functional initiator residue at the α-chain end. Kinetic and block copolymerization experiments demonstrated that the SCTP of M2 proceeded in a chain-growth and controlled/living polymerization manner. This is a novel study on the synthesis of 2,7-PCz via SCTP. By taking advantage of the well-controlled nature of this polymerization system, we demonstrated the synthesis of high-molecular-weight 2,7-PCzs (M_n = 5–38 kg mol⁻¹) with a relatively narrow Ð_M (1.35–1.48). Furthermore, we successfully synthesized fluorene/carbazole copolymers as well as 2,7-PCz-containing diblock copolymers, demonstrating the versatility of the present polymerization system as a novel synthetic strategy for well-defined polycarbazole-based materials. Full article

Five carbazole-containing polymeric membranes (PDTC, P(DTC-co-BTP), P(DTC-co-BTP2), P(DTC-co-TF), and P(DTC-co-TF2)) were electrodeposited on transparent conductive electrodes. P(DTC-co-BTP2) shows a high ΔT (68.4%) at 855 nm. The multichromic properties of P(DTC-co-TF2) membrane range between dark yellow, yellowish-green, gunmetal gray, and dark gray in various reduced and oxidized states. Polymer-based organic electrochromic devices are assembled using 2,2′-bithiophene- and 2-(2-thienyl)furan-based copolymers as anodic membranes, and poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) as the cathodic membrane. P(DTC-co-TF)/PEDOT-PSS electrochromic device (ECD) displays a high transmittance change (ΔT%) (43.4%) at 627 nm as well as a rapid switching time (less than 0.6 s) from a colored to a bleached state. Moreover, P(DTC-co-TF2)/PEDOT-PSS ECD shows satisfactory optical memory (the transmittance change is less than 2.9% in the colored state) and high coloration efficiency (512.6 cm² C⁻¹) at 627 nm. Full article

A series of carbazole-based polymers (PdCz, P(dCz2-co-dTC1), P(dCz2-co-dTC2), P(dCz1-co-dTC2), and PdTC) were deposited on indium tin oxide (ITO) conductive electrodes using electrochemical polymerization. The as-prepared P(dCz2-co-dTC2) displayed a high ΔT (57.0%) and multichromic behaviors ranging from yellowish green, greenish gray, gray to purplish gray in different redox states. Five organic electrochromic devices (ECDs) were built using dCz- and dTC-containing homopolymers and copolymers as anodic materials, and poly(3,4-(2,2-dimethylpropylenedioxy)thiophene) (PProdot-Me₂) as the cathodic material. The P(dCz2-co-dTC2)/PProdot-Me₂ ECD presented remarkable electrochromic behaviors from the bleached to colored states. Moreover, P(dCz2-co-dTC2)/PProdot-Me₂ ECD displayed a high optical contrast (ΔT, 45.8%), short switching time (ca. 0.3 s), high coloration efficiency (528.8 cm² C⁻¹) at 580 nm, and high redox cycling stability. Full article

Synthesis of novel block and random copolymers, containing a carbazole unit and (di)phenylanthracene moiety in the side chains, has been described in this paper. Block and random copolymers composed of 4-bromophenyl vinyl sulfide (BPVS) and N-vinylcarbazole (NVC) were initially prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. Then, anthracene-based groups were introduced on the bromophenyl unit in the carbazole-containing copolymers by Pd-catalyzed coupling to yield functional copolymers with additional (di)phenylanthracene units. The resulting copolymers, having two distinct electronic functionalities, exhibited characteristic fluorescence resonance energy transfer, as confirmed by UV-vis and fluorescence spectra. Full article

The presented study describes the method for the synthesis and characterization of a new class of conjugated copolymers containing a perylenediimide (PDI) and naphthalene diimide (NDI) side groups. The main conjugated backbone is a donor-acceptor polymer poly[3,6-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] containing thiophene and carbazole as donor units and benzothiadiazole as an acceptor unit. The presented compounds were synthesized in a multistep synthesis. The polymerization was carried out by Suzuki or Stille coupling reaction. Redox properties of the studied polymers were tested in different conditions. Electrochemical investigation revealed independent reduction of the main polymer chain and diimide side groups. UV-Vis spectroscopy revealed the overlap of two absorption spectra. The difference between the electron affinity of the polymer main chain and that of the diimides estimated electrochemically is approximately 0.3 eV. Full article