Molecular electrets – Why do dipoles matter for charge transfer and excited-state dynamics?

Rybicka‐Jasińska, Katarzyna; Vullev, Valentine I.

doi:10.1016/j.jphotochem.2020.112779

Cited by 5 publications

(7 citation statements)

References 92 publications

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“…Charge transfer ( q CT ) and distance of charge transfer ( D CT ) remain at the core and play a pivotal role in the energy conversion from light harvesting to energy storage . In natural photosynthesis, long-range (LR) electron transfers occur rapidly between donor–acceptor pairs within the protein matrix .…”

Section: Introductionmentioning

confidence: 99%

“…In natural photosynthesis, long-range (LR) electron transfers occur rapidly between donor–acceptor pairs within the protein matrix . Regular amide bonds coupled with hydrogen bonding in proteins induce electric dipoles, offering electron transfer and aiding ion transport. − However, employing protein-based moieties in organic solar cells (OSCs) to achieve higher q CT and D CT is met with many practical challenges. Larger lowest unoccupied molecular orbital (LUMO)–highest occupied molecular orbital (HOMO) gaps and inaccessible reduction potentials render these bimolecular systems ineffective for electronic applications .…”

Section: Introductionmentioning

confidence: 99%

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Novel Donor–Electret–Acceptor Framework for Higher Charge Transfer and Distance of Charge Transfer through Dipole Engineering

Vikramaditya

Lin

2021

J. Phys. Chem. C

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Solar cells try to mimic the natural process of photosynthesis to convert light energy into electrical energy. Longrange electron transfers occur rapidly between donor−acceptor pairs within the protein matrix. However, protein-based moieties are not suited for electronic applications. The widely employed donor− (bridge) n −acceptor (DB n A; n ≥ 1) framework typically fails to effectively transfer the charge over longer distances, leading to larger exciton binding energies and lower power conversion efficiencies in organic solar cells. By modifying the dipole neutral bridge into an electret, we propose a donor−electret n −acceptor (DE n A; n ≥ 1) model, which addresses the limitations of the conventional donor− bridge−acceptor (DBA) architecture. We design a novel electret based on an aromatic-5-membered ring (A5R) substituted with polar groups in a stereoregular fashion. Due to the peculiar symmetry offered by the A5R and the asymmetry achieved through the regioregular substitution of polar groups, a co-directional dipole is induced along the electret backbone. Exploiting this unique behavior and orienting the dipole direction of the electret opposite to the donor−acceptor duo in the donor−electret−acceptor (DEA) framework, higher magnitudes of charge transfer (q CT ) and distance of charge transfer (D CT ) are realized. This novel design offers the following: (1) Higher q CT and D CT are achieved, which overcomes the inherent length dependency of DBAs with increasing chain length. (2) D CT over ∼12 Å and beyond is possible with the proposed DEA architecture, which can compete with the natural protein helix in efficient electron transfer and exciton dissociation. (3) The electret allows us to tune the ground-state (GS) dipole without compromising on higher q CT and D CT properties; the lower GS dipole enables the solubility of DEAs in mild solvents. (4) Higher degrees of freedom in the substitution patterns provided by the electret allow us to alter not only q CT and D CT but also other electronic and optical properties including lowest unoccupied molecular orbital−highest occupied molecular orbital gaps, optical gaps, dipoles, oscillator strengths, and so on.(5) A new window in exploiting the substitution patterns provided by the electret to design novel materials is opened, which have potential applications in diverse areas. Our density functional theory/time-dependent density functional theory studies employing optimally tuned range-separated hybrids predict accurate optical properties against the experimental results.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Novel Donor–Electret–Acceptor Framework for Higher Charge Transfer and Distance of Charge Transfer through Dipole Engineering

Vikramaditya

Lin

2021

J. Phys. Chem. C

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“…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%

“…Considering the desirable features of these two completely different classes of biomolecules (i.e., protein helices and DNA/PNA strands), we designed bioinspired molecular electrets based on anthranilamide (Aa) structural motifs ( Figure 1 ) [ 28 ].…”

Section: Introductionmentioning

confidence: 99%

“…A principal task in this line of research was making the Aa bioinspired molecules [ 28 , 29 ], which is the focus of this publication. While they are polypeptides of aromatic β-amino acids, none of the strategies for chemical or biochemical synthesis of biological and biomimetic peptides works for making Aa conjugates ( Figure 2 a) [ 29 ].…”

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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Bias dependent dipolar electric field at self-assembled monolayer (SAM)/organic interface determines the hole drift mobility

Cvikl

2023

Synthetic Metals

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Molecular electrets – Why do dipoles matter for charge transfer and excited-state dynamics?

Cited by 5 publications

References 92 publications

Novel Donor–Electret–Acceptor Framework for Higher Charge Transfer and Distance of Charge Transfer through Dipole Engineering

Novel Donor–Electret–Acceptor Framework for Higher Charge Transfer and Distance of Charge Transfer through Dipole Engineering

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

Bias dependent dipolar electric field at self-assembled monolayer (SAM)/organic interface determines the hole drift mobility

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