Multifaceted aspects of charge transfer

Derr, James B.; Tamayo, Jesse; Clark, John A.; Morales, Maryann; Mayther, Maximillian F.; Espinoza, Eli M.; Rybicka‐Jasińska, Katarzyna; Vullev, Valentine I.

doi:10.1039/d0cp01556c

Cited by 30 publications

(45 citation statements)

References 752 publications

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“…In its many forms, charge transfer (CT) is the fundamental process that sustains life on Earth and makes our modern ways of living possible [ 1 ]. Biological, biomimetic, and bioinspired systems encompass some of the most important templates for advancing CT science and engineering [ 2 ].…”

Section: Introductionmentioning

confidence: 99%

“…The Marcus semiclassical transition-state theory has revolutionized the understanding of biological CT and bioenergetics at a molecular level [ 3 ]. The diabatic nature of CT mediated by biomolecules has made Marcus-Hush and Marcus-Levich-Jortner formalisms perfect for the analysis of such systems [ 1 ]. At the same time, biological CT has driven the evolution of CT science, resulting in new theories and unprecedented ways of thinking [ 4 , 5 , 6 , 7 , 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

“…In the 1990s, CT through biological and bioinspired molecules provided the experimental evidence for such effects [ 13 , 14 , 15 , 16 ]. As the field took off, the focus was on dipolar biomolecules on one hand, and on small polar organic conjugates on the other, limiting the range of CT to 2 nm, and the mechanism predominantly to tunneling or superexchange [ 1 , 6 , 10 ]. To take the field out of this confinement, we developed the concept for CT bioinspired molecular electrets ( Figure 1 ) [ 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ].…”

Section: Introductionmentioning

confidence: 99%

“…Electron-donating R 2 substituents stabilize the radical cations of such Aa residues by pulling the spin density away from their C-terminal amides, making them excellent candidates for mediating hole transfer via long-range hopping. Electron-donating substituents, however, also lower the reduction potentials of these radical cations, precluding the transduction of holes with high enough energy to drive certain chemical transformations or to ensure large voltages at the termini of energy-conversion devices [ 1 , 43 , 44 ]. Therefore, we focused on ether-functionalized Aa conjugates.…”

Section: Introductionmentioning

confidence: 99%

“…Addition of the residue building blocks such as NBA derivatives via a sequence of amide-coupling and nitro-reduction steps yields Aa oligomers of different lengths and complexity [ 29 ]. Alkyloxy derivatives of NBA are essential for building ether-functionalized Aa conjugates to serve as molecular electrets that can mediate the transfer of high-energy holes via hopping (i.e., incoherent CT that has the key advantage of covering long distances) [ 1 ]. The capability to make highly pure NBA derivatives in large quantities, with as few synthetic and purification steps as possible, is essential for advancing the pursuit for new Aa bioinspired molecular electrets.…”

Section: Introductionmentioning

confidence: 99%

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On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials

et al. 2021

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Biological structure-function relationships offer incomparable paradigms for charge-transfer (CT) science and its implementation in solar-energy engineering, organic electronics, and photonics. Electrets are systems with co-directionally oriented electric dopes with immense importance for CT science, and bioinspired molecular electrets are polyamides of anthranilic-acid derivatives with designs originating from natural biomolecular motifs. This publication focuses on the synthesis of molecular electrets with ether substituents. As important as ether electret residues are for transferring holes under relatively high potentials, the synthesis of their precursors presents formidable challenges. Each residue in the molecular electrets is introduced as its 2-nitrobenzoic acid (NBA) derivative. Hence, robust and scalable synthesis of ether derivatives of NBA is essential for making such hole-transfer molecular electrets. Purdie-Irvine alkylation, using silver oxide, produces with 90% yield the esters of the NBA building block for iso-butyl ether electrets. It warrants additional ester hydrolysis for obtaining the desired NBA precursor. Conversely, Williamson etherification selectively produces the same free-acid ether derivative in one-pot reaction, but a 40% yield. The high yields of Purdie-Irvine alkylation and the selectivity of the Williamson etherification provide important guidelines for synthesizing building blocks for bioinspired molecular electrets and a wide range of other complex ether conjugates.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials

et al. 2021

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Chances and challenges of long‐distance electron transfer for cellular redox reactions

2022

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Biological redox reactions often use a set‐up in which final redox partners are localized in different compartments and electron transfer (ET) among them is mediated by redox‐active molecules. In enzymes, these ET processes occur over nm distances, whereas multi‐protein filaments bridge μm ranges. Electrons are transported over cm ranges in cable bacteria, which are formed by thousands of cells. In this review, we describe molecular mechanisms that explain how respiration in a compartmentalized set‐up ensures redox homeostasis. We highlight mechanistic studies on ET through metal‐free peptides and proteins demonstrating that long‐distance ET is possible because amino acids Tyr, Trp, Phe, and Met can act as relay stations. This cuts one long ET into several short reaction steps. The chances and challenges of long‐distance ET for cellular redox reactions are then discussed.

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Charge‐Transfer Modulation of Emissivity in Polarized Diketopyrrolopyrroles

Kumar,

Banasiewicz,

et al. 2024

ChemPhotoChem

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Strongly polarized donor‐acceptor‐donor′ diketopyrrolopyrroles, differing in the type of key donor moiety, were designed and synthesized to examine how this affects the non‐radiative decay. Dyes possessing less electron‐rich N‐carbazolyl substituents are characterized by strong yellow emission from a locally excited (LE) state, whereas replacing this donor with more electron‐rich N‐phenothiazinyl substituent changes the relative position of CT and LE states, leading to weaker, reddish‐orange fluorescence. As a result, there is solvent‐dependent charge‐transfer emission shifted to as far as 700 nm. The opening of the intersystem crossing channel to the triplet state possessing CT character is the most likely cause of the fluorescence quantum yield variation in some cases. These results reveal that the fate of molecules in their excited state can be fine‐tuned by very small structural changes.

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Multifaceted aspects of charge transfer

Abstract: Charge transfer and charge transport are by far among the most important processes for sustaining life on Earth and for making our modern ways of living possible. Involving multiple electron-transfer...

Cited by 30 publications

References 752 publications

On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials

On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials

Chances and challenges of long‐distance electron transfer for cellular redox reactions

Charge‐Transfer Modulation of Emissivity in Polarized Diketopyrrolopyrroles

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