Synthesis, photophysical, electrochemical, and DSSC application of novel donor–acceptor triazole bridged dendrimers with a triphenylamine core and benzoheterazole as a surface unit

Rajavelu, Kannan; Rajakumar, Perumal; Mandal, Sudip; Ramanujam, Kothandaraman

doi:10.1039/c6nj02126c

Cited by 14 publications

(5 citation statements)

References 62 publications

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“…In comparison, the [M(HL)] + complexes in acetonitrile solution showed analogous vibrational bands, which were also confirmed by DFT simulations, although these occurred at slightly higher Raman shifts than for the immobilized complexes (Tables S8 and S11, respectively). No 1,2,3-triazole ring centered peaks were observed in the Raman spectra, which is not as surprising as it might seem, as 1,2,3-triazole rings are known to not be particularly Raman active due to the lack of charge transfer between the PEDOT backbone and the clicked complexes, 65,66 and this was confirmed by DFT simulations (Table S11). Raman spectroelectrochemistry measurements, in combination with DFT simulations, also confirmed that the metal complexes been immobilized onto the polymer films, and demonstrated that the clicked M@tz-PEDOT films are also able to undergo the usual PEDOT doping/de-doping processes without any impediment from the attached metal complexes.…”

Section: Acs Appliedsupporting

confidence: 53%

Electroactive Metal Complexes Covalently Attached to Conductive PEDOT Films: A Spectroelectrochemical Study

Rodríguez‐Jiménez

Bennington

Akbarinejad

et al. 2020

ACS Appl. Mater. Interfaces

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The successful covalent attachment, via copper(I)-catalyzed azide alkyne cycloaddition (CuAAC), of alkyne-functionalized nickel(II) and copper(II) macrocyclic complexes onto azide (N3)-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films on ITO-coated glass electrodes is reported. To investigate the surface attachment of the selected metal complexes, which are analogues of the cobalt-based complex previously reported to be a molecular catalyst for hydrogen evolution, first, three different PEDOT films were formed by electropolymerization of pure PEDOT or pure N3-PEDOT, and last, 1:2N3-PEDOT:PEDOT were formed by co-polymerizing a 1:4 mixture of N3-EDOT:EDOT monomers. The successful surface immobilization of the complexes on the latter two azide-functionalized films, by CuAAC, was confirmed by X-ray photoelectron spectroscopy (XPS) and electrochemistry as well as by UV–vis–NIR and resonance Raman spectroelectrochemistry. The ratio between the N3 groups, and hence, the number of surface-attached metal complexes after CuAAC functionalization, in pristine N3-PEDOT versus 1:2N3-PEDOT:PEDOT is expected to be 3:1 and seen to be 2.86:1 with a calculated surface coverage of 3.28 ± 1.04 and 1.15 ± 0.09 nmol/cm2, respectively. The conversion, to the metal complex attached films, was lower for the N3-PEDOT films (Ni 74%, Cu 76%) than for the copolymer 1:2N3-PEDOT:PEDOT films (Ni 83%, Cu 91%) due to the former being more sterically congested. The Raman and UV–vis–NIR results were simulated using density functional theory (DFT) and time-dependent DFT (TD-DFT), respectively, and showed good agreement with the experimental data. Importantly, the spectroelectrochemical behavior of both anchored metal complexes is analogous to that of the free metal complexes in solution. This proves that PEDOT films are promising conducting scaffolds for the covalent immobilization of metal complexes, as the existing electrochromic features of the complexes are preserved on immobilization, which is important for applications in electrocatalytic proton and carbon dioxide reduction, optoelectronics, and sensing.

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Section: Acs Appliedsupporting

confidence: 53%

Electroactive Metal Complexes Covalently Attached to Conductive PEDOT Films: A Spectroelectrochemical Study

Rodríguez‐Jiménez

Bennington

Akbarinejad

et al. 2020

ACS Appl. Mater. Interfaces

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“…Modified triphenylamines with various numbers of o -carborane units were synthesized ( Figure 1 and Scheme 1 ) [ 48 ]. The desired products were obtained via insertion of decaborane(14) to ethynyl compounds.…”

Section: Resultsmentioning

confidence: 99%

Enhancement of Aggregation-Induced Emission by Introducing Multiple o-Carborane Substitutions into Triphenylamine

et al. 2017

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The enhancement of aggregation-induced emission (AIE) is presented on the basis of the strategy for improving solid-state luminescence by employing multiple o-carborane substituents. We synthesized the modified triphenylamines with various numbers of o-carborane units and compared their optical properties. From the optical measurements, the emission bands from the twisted intramolecular charge transfer (TICT) state were obtained from the modified triphenylamines. It was notable that emission efficiencies of the multi-substituted triphenylamines including two or three o-carborane units were enhanced 6- to 8-fold compared to those of the mono-substituted triphenylamine. According to mechanistic studies, it was proposed that the single o-carborane substitution can load the AIE property via the TICT mechanism. It was revealed that the additional o-carborane units contribute to improving solid-state emission by suppressing aggregation-caused quenching (ACQ). Subsequently, intense AIEs were obtained. This paper presents a new role of the o-carborane substituent in the enhancement of AIEs.

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“…Therefore, PTA-NPs are very promising for photothermal cancer therapy in preclinical applications. (10) [35], 4-bromo-N,N-diphenyl aniline (6) [36], and 4-ethynyl-N,N-diphenylaniline (7) [37] were prepared according to methods in the literature (Scheme S1).…”

Section: Introductionmentioning

confidence: 99%

Organic Nanoparticles Based on D-A-D Small Molecule: Self-Assembly, Photophysical Properties, and Synergistic Photodynamic/Photothermal Effects

Yue

Sun

et al. 2022

Materials

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Cancer is one of the major diseases threatening human health. Traditional cancer treatments have notable side-effects as they can damage the immune system. Recently, phototherapy, as a potential strategy for clinical cancer therapy, has received wide attention due to its minimal invasiveness and high efficiency. Herein, a small organic molecule (PTA) with a D-A-D structure was prepared via a Sonogashira coupling reaction between the electron-withdrawing dibromo-perylenediimide and electron-donating 4-ethynyl-N,N-diphenylaniline. The amphiphilic organic molecule was then transformed into nanoparticles (PTA-NPs) through the self-assembling method. Upon laser irradiation at 635 nm, PTA-NPs displayed a high photothermal conversion efficiency (PCE = 43%) together with efficient reactive oxygen species (ROS) generation. The fluorescence images also indicated the production of ROS in cancer cells with PTA-NPs. In addition, the biocompatibility and photocytotoxicity of PTA-NPs were evaluated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and live/dead cell co-staining test. Therefore, the as-prepared organic nanomaterials were demonstrated as promising nanomaterials for cancer phototherapy in the clinic.

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Synthesis, photophysical, electrochemical, and DSSC application of novel donor–acceptor triazole bridged dendrimers with a triphenylamine core and benzoheterazole as a surface unit

Abstract: Triazole bridged novel donor–acceptor dendrimers were synthesized via click chemistry. Lower generation dendrimers when used as additives exhibit better current-generating capacity and power conversion efficiency in DSSCs.

Cited by 14 publications

References 62 publications

Electroactive Metal Complexes Covalently Attached to Conductive PEDOT Films: A Spectroelectrochemical Study

Electroactive Metal Complexes Covalently Attached to Conductive PEDOT Films: A Spectroelectrochemical Study

Enhancement of Aggregation-Induced Emission by Introducing Multiple o-Carborane Substitutions into Triphenylamine

Organic Nanoparticles Based on D-A-D Small Molecule: Self-Assembly, Photophysical Properties, and Synergistic Photodynamic/Photothermal Effects

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