Spectroscopic, electrochemical and electrocolorimetric properties of novel 2-(2′-pyridyl)-1H-benzimidazole appended bay-substituted perylene diimide triads

Pekdemir, Fatih; Orman, Efe Baturhan; Selçuki, Nursel Açar; Özkaya, Ali Rıza; Salih, Bekir; Şengül, Abdurrahman

doi:10.1016/j.jphotochem.2019.04.039

Cited by 7 publications

(6 citation statements)

References 47 publications

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“…At the same time, two strong absorption bands appeared at 617 and 652 nm. The observed orange to green to blue color change was consistent for bpy-C2-NPDI , Re(bpy-C4-NPDI) , and Re(bpy-C6-NPDI) (Figures S92–S95), further confirming the assignment of the PDI 0/•– and PDI •–/2– reductions. , Moreover, application of potentials of −0.9 V (R1) and −1.2 V (R2) led to similar UV–vis-nIR SEC responses for Re(py-C0-NPDI) (Figure S96). However, differences in the absorption profiles of Re(py-C0-NPDI) vs Re(bpy-C2/4/6-NPDI) meant each transition was broadened and found to occur at a slightly blue-shifted λ max .…”

Section: Resultssupporting

confidence: 74%

“…Re(bpy-C2-NPDI) −1. 72,81 Moreover, application of potentials of −0.9 V (R1) and −1.2 V (R2) led to similar UV− vis-nIR SEC responses for Re(py-C0-NPDI) (Figure S96). However, differences in the absorption profiles of Re(py-C0-NPDI) vs Re(bpy-C2/4/6-NPDI) meant each transition was broadened and found to occur at a slightly blue-shifted λ max .…”

Section: ■ Introductionmentioning

confidence: 84%

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Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

et al. 2021

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We report the design, synthesis, and characterization of four N-annulated perylene diimide (NPDI) functionalized rhenium bipyridine [Re(bpy)] supramolecular dyads. The Re(bpy) scaffold was connected to the NPDI chromophore either directly [Re(py-C0-NPDI)] or via an ethyl [Re(bpy-C2-NPDI)], butyl [Re(bpy-C4-NPDI)], or hexyl [Re(bpy-C6-NPDI)] alkyl-chain spacer. Upon electrochemical reduction in the presence of CO2 and a proton source, Re(bpy-C2/4/6-NPDI) all exhibited significant current enhancement effects, while Re(py-C0-NPDI) did not. During controlled potential electrolysis (CPE) experiments at E appl = −1.8 V vs Fc+/0, Re(bpy-C2/4/6-NPDI) all achieved comparable activity (TONco ∼ 25) and Faradaic efficiency (FEco ∼ 94%). Under identical CPE conditions, the standard catalyst Re(dmbpy) was inactive for electrocatalytic CO2 reduction; only at E appl = −2.1 V vs Fc+/0 could Re(dmbpy) achieve the same catalytic performance, representing a 300 mV lowering in overpotential for Re(bpy-C2/4/6-NPDI). At higher overpotentials, Re(bpy-C4/6-NPDI) both outperformed Re(bpy-C2-NPDI), indicating the possibility of coinciding electrocatalytic CO2 reduction mechanisms that are dictated by tether-length and overpotential. Using UV-vis-nearIR spectroelectrochemistry (SEC), FTIR SEC, and chemical reduction experiments, it was shown that the NPDI-moiety served as an electron-reservoir for Re(bpy), thereby allowing catalytic activity at lower overpotentials. Density functional theory studies probing the optimized geometries and frontier molecular orbitals of various catalytic intermediates revealed that the geometric configuration of NPDI relative to the Re(bpy)-moiety plays a critical role in accessing electrons from the electron-reservoir. The improved performance of Re(bpy-C2/4/6-NPDI)dyads at lower overpotentials, relative to Re(dmbpy), highlights the utility of chromophore electron-reservoirs as a method for lowering the overpotential for CO2 conversion.

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Section: Resultssupporting

confidence: 74%

Section: ■ Introductionmentioning

confidence: 84%

Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

et al. 2021

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“…MESP mapping is very useful in investigating the physicochemical properties of molecular structure. 31 A portion of the molecule with negative electrostatic potential is sensitive to electrophilic attack.…”

Section: Molecular Electrostatic Potential Surface (Mesp)mentioning

confidence: 99%

Molecular structure, frontier molecular orbitals, NBO, MESP and thermodynamic properties of 5,12-dibromo perylene with DFT calculation methods

Akman

Ata

Yıldıko

et al. 2020

International Journal of Chemistry and Technology

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Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) has been used as industrial pigments for many years. This perspective makes it important to determine the synthesis and physical properties of PTCDA derivatives and their functional properties for application as electron acceptors in organic transistors. In the gas phase, the quantum chemical study of the 5,12-dibromoperylene compound was performed using the basic set of LanL2DZ and 6-311G of the density function theory (DFT)-B3LYP method. Because basic set of LanL2DZ and 6-311G of the density function theory (DFT)-B3LYP method are predicted to yield more efficient and verifiable results than others. 1 H-NMR, 13 C-NMR, HOMO-LUMO analysis, dipole moment, molecular electrostatic surface potential (MESP) and natural orbital bond (NBO) analysis of the molecule were carried out. The results were shown with graphs, tables and figures. In the comparison of 1 H-NMR, 13 C-NMR results with the experimental values, B3LYP 6-311G gave more successful results. The nonlinear optical properties of the compound were determined.

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“…This same color change was observed with bpy-TAz-PDI (Figure S35), confirming the assignment of a PDI 0/•─ reduction. 74 Decreasing the potential to -1.5 V (R2) caused the solution to progress from green to blue. During this color change, the λmax at 690 nm partially decreased while the absorption fine-structure in the near-IR essentially disappeared.…”

Section: ▪ Mechanistic Investigationmentioning

confidence: 99%

Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

Koenig¹,

Dubrawski²,

Rao³

et al. 2020

Preprint

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Here we report on a molecular catalyst with a built-in electron-reservoir for enhanced CO2 conversion. The synthesis and characterization of this N-annulated perylene diimide (PDI) photosensitized Re(bpy) supramolecular dyad [Re(bpy-TAz-PDI)], as well as successful electro- and photocatalytic CO2-to-CO conversion, are detailed herein. Upon electrochemical reduction in the presence of CO2 and a proton source, Re(bpy-TAz-PDI) exhibited significant current enhancement, where the onset of electrocatalytic CO2 reduction for Re(bpy-TAz-PDI) occurred at a much less negative potential than standard Re(bpy) complexes. At an applied potential of -1.8 V vs. Fc+/0, 400 mV lower than the benchmark Re(dmbpy) catalyst, Re(bpy-TAz-PDI) was able to achieve the same catalytic activity (TONco = 24) and Faradaic efficiency (FE = 92 %) during controlled potential electrolysis (CPE) experiments. Through a combination of UV-visible-nearIR spectroelectrochemistry (SEC), FTIR SEC, and chemical reduction experiments, it was shown that the PDI-moiety served as an electron-reservoir for Re(bpy), thereby allowing catalytic activity at lower overpotentials. Density functional theory (DFT) studies probing the optimized geometries, frontier molecular orbitals, and spin-densities of various catalytic intermediates revealed that the geometric configuration of PDI, relative to the Re(bpy)-moiety, plays a critical role in accessing electrons from the electron-reservoir. The near identical performance of Re(bpy-TAz-PDI) at lower overpotentials relative to the benchmark Re(dmbpy) catalyst highlights the utility of organic chromophore electron-reservoirs as a method for lowering the required overpotential for CO2 conversion. <br>

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Spectroscopic, electrochemical and electrocolorimetric properties of novel 2-(2′-pyridyl)-1H-benzimidazole appended bay-substituted perylene diimide triads

Cited by 7 publications

References 47 publications

Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

Molecular structure, frontier molecular orbitals, NBO, MESP and thermodynamic properties of 5,12-dibromo perylene with DFT calculation methods

Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

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Spectroscopic, electrochemical and electrocolorimetric properties of novel 2-(2′-pyridyl)-1H-benzimidazole appended bay-substituted perylene diimide triads

Cited by 7 publications

References 47 publications

Lowering Electrocatalytic CO2 Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

Lowering Electrocatalytic CO2 Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

Molecular structure, frontier molecular orbitals, NBO, MESP and thermodynamic properties of 5,12-dibromo perylene with DFT calculation methods

Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

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Product

Resources

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Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

Lowering Electrocatalytic CO₂ Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length