Solvent-dependent ground-state distributions in a donor-acceptor redox-active bistable [2]catenane

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side‑products. This is particularly important for bioelectronic devices which are designed to operate in biological systems. While redox‑active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‑reactions with molecular oxygen during device operation. We show that this electrochemical side reaction yields hydrogen peroxide (H2O2), a reactive side‑product, which may be harmful to the local biological environment and may also accelerate device degradation. We report a design strategy for the development of redox-active organic semiconductors based on donor-acceptor copolymers that prevent the formation of H2O2 during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‑gated devices in application-relevant environments.

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Metal-Free Catalysis: A Redox-Active Donor–Acceptor Conjugated Microporous Polymer for Selective Visible-Light-Driven CO2 Reduction to CH4

Journal of the American Chemical Society ◽

10.1021/jacs.1c07916 ◽

2021 ◽

Author(s):

Soumitra Barman ◽

Ashish Singh ◽

Faruk Ahamed Rahimi ◽

Tapas Kumar Maji

Keyword(s):

Visible Light ◽

Co2 Reduction ◽

Metal Free ◽

Conjugated Microporous Polymer ◽

Redox Active ◽

Microporous Polymer ◽

Visible Light Driven ◽

Donor Acceptor ◽

Active Donor

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Inversion of donor–acceptor roles in photoinduced intervalence charge transfers

Chemical Communications ◽

10.1039/c9cc03483h ◽

2019 ◽

Vol 55 (53) ◽

pp. 7659-7662 ◽

Cited By ~ 3

Author(s):

Bruno M. Aramburu-Trošelj ◽

Paola S. Oviedo ◽

Ivana Ramírez-Wierzbicki ◽

Luis M. Baraldo ◽

Alejandro Cadranel

Keyword(s):

Electron Donor ◽

Electron Acceptor ◽

Ground State ◽

Mixed Valence ◽

Donor Acceptor

Upon MLCT photoexcitation, {(tpy)Ru} becomes the electron acceptor in the mixed valence {(tpy˙−)RuIII−δ-NC-MII+δ} moiety, reversing its role as the electron donor in the ground-state mixed valence analogue.

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Halogen-Bond Assisted Photoinduced Electron Transfer

Molecules ◽

10.3390/molecules24234361 ◽

2019 ◽

Vol 24 (23) ◽

pp. 4361

Author(s):

Bogdan Dereka ◽

Ina Fureraj ◽

Arnulf Rosspeintner ◽

Eric Vauthey

Keyword(s):

Electron Transfer ◽

Excited State ◽

Ground State ◽

Halogen Bond ◽

Quenching Rate ◽

Excited Complex ◽

Diffusion Controlled ◽

Donor Acceptor ◽

Quenching Rate Constant ◽

Excited State Population

The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor–donor–acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927–3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski–Collins–Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.

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Multi-mode ground state interaction terms in C60-based electron donor-acceptor complexes

Open Physics ◽

10.2478/bf02475634 ◽

2004 ◽

Vol 2 (2) ◽

Cited By ~ 1

Author(s):

Elena Sheka

Keyword(s):

Ground State ◽

Singlet State ◽

Molecular Complexes ◽

Suggested Approach ◽

Interaction Terms ◽

Binary Complexes ◽

Avoided Crossing ◽

Donor Acceptor ◽

Multi Mode ◽

Chemical Testing

AbstractQuantum-chemical testing of donor-acceptor properties of binary molecular complexes, related to the singlet state, is suggested as QCh calculations of studied systems and their constituents by using both spin-nondependent (RHF) and spindependent (UHF) versions of the exploited computational tool. The avoided crossing of intermolecular interaction terms of neutral moleculesE int(A 0 B 0) and molecular ionsE int(A + B −) causes a multi-mode character of the ground state term. The dependence of D-A complex properties on the type of the term, space positions of the term minimum, and the interrelation of the corresponding energies are discussed. The suggested approach has been applied to binary complexes C60+X (X=TAE, TDAE, DMMA, COANP, 2Li, Mg).

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Redox-active and semi-conducting donor–acceptor conjugated microporous polymers as metal-free ORR catalysts

Journal of Materials Chemistry A ◽

10.1039/c8ta00099a ◽

2018 ◽

Vol 6 (14) ◽

pp. 5587-5591 ◽

Cited By ~ 24

Author(s):

Syamantak Roy ◽

Arkamita Bandyopadhyay ◽

Mrinmay Das ◽

Partha Pratim Ray ◽

Swapan K. Pati ◽

...

Keyword(s):

Oxygen Reduction ◽

Metal Free ◽

Microporous Polymers ◽

Redox Active ◽

Donor Acceptor ◽

Electrochemical Oxygen ◽

Conjugated Microporous Polymers

Donor–acceptor CMPs showing inherent conductivity and electrochemical oxygen reduction.

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Ground-state electron transfer in all-polymer donor–acceptor heterojunctions

Nature Materials ◽

10.1038/s41563-020-0618-7 ◽

2020 ◽

Vol 19 (7) ◽

pp. 738-744 ◽

Cited By ~ 14

Author(s):

Kai Xu ◽

Hengda Sun ◽

Tero-Petri Ruoko ◽

Gang Wang ◽

Renee Kroon ◽

...

Keyword(s):

Electron Transfer ◽

Ground State ◽

State Electron ◽

Donor Acceptor ◽

Ground State Electron

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A 2D donor–acceptor covalent organic framework with charge transfer for supercapacitors

Chemical Communications ◽

10.1039/d0cc04109b ◽

2020 ◽

Vol 56 (91) ◽

pp. 14187-14190

Author(s):

Tao Li ◽

Xiaodong Yan ◽

Wen-Da Zhang ◽

Wang-Kang Han ◽

Yong Liu ◽

...

Keyword(s):

Electrical Conductivity ◽

Charge Transfer ◽

Energy Density ◽

Specific Capacitance ◽

Intramolecular Charge Transfer ◽

High Electrical Conductivity ◽

Covalent Organic Framework ◽

Redox Active ◽

Donor Acceptor ◽

Organic Framework

A 2D covalent organic framework with intramolecular charge transfer, numerous redox-active groups and high electrical conductivity possesses a specific capacitance of 752 F g−1 and an energy density of 57 W h kg−1.

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