Quantifying Planarity in the Design of Organic Electronic Materials

Che, Yuxuan; Perepichka, Dmitrii F.

doi:10.1002/ange.202011521

Cited by 3 publications

(3 citation statements)

References 64 publications

(120 reference statements)

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“…We envisaged that an increase of the interplanar angle (φ DA ) between the anion and the cation moieties of 1a derivatives would decrease E Int . We then designed the π-conjugated zwitterions 2a – 4a by the benzoannulation to 1a because φ DA would be increased by the steric hindrance (Figure ).…”

Section: Introductionmentioning

confidence: 99%

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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π-Conjugated molecules with small highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) energy gaps (ΔE H−L ) have been extensively studied because of their unique optoelectronic properties. Although the expansion of πconjugation is one of the well-known approaches for designing molecules with small ΔE H−L values, such an approach inevitably gives large πconjugated molecules sometimes suffering from synthetic difficulty and low solubility toward organic solvents. To develop relatively small donor− acceptor molecules with small ΔE H−L values, we have designed and synthesized π-conjugated zwitterions composed of electron-donating anions, such as phenoxide and anthroxide, and electron-accepting cations, such as pyridinium and acridinium. The energy difference between the HOMO of the anion and the LUMO of the cation (ΔE D−A ) and the interplanar angle between them (φ DA ) have a crucial effect on ΔE H−L , and hence, on the electronic structures and optoelectronic properties of these zwitterions. The zwitterions with small ΔE D−A and large φ DA have a small ΔE H−L of ca. 1 eV and show amphoteric redox properties and near-infrared (NIR) electronic absorption exceeding λ = 1000 nm. The NIR absorption responds to solvent polarity, temperature, and acid addition. This molecular design will generate small π-conjugated donor−acceptor molecules with small ΔE H−L values.

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Section: Introductionmentioning

confidence: 99%

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

et al. 2020

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“…Then, we performed DFT calculations to estimate the planarity of the polymer building block combinations by using a recently developed planarity indexes ⟨cos 2 φ⟩ 30 . We found that TDPP can form planar polymer backbone with TQ and BBT with high torsional barriers and large ⟨cos 2 φ⟩ (Fig.…”

Section: Resultsmentioning

confidence: 99%

High-mobility semiconducting polymers with different spin ground states

Chen¹,

Li²,

Fang³

et al. 2021

Preprint

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Organic semiconductors with high-spin ground states are fascinating because they could enable fundamental understanding on spin-related phenomenon in light element and provide opportunities for organic magnetic and quantum materials. Although high-spin ground states have been observed in some quinoidal type small molecules or doped organic semiconductors, semiconducting polymers with high-spin at its neutral ground state are rarely reported because of the less of clear design strategy. Here we propose a molecular design strategy to obtain high-mobility semiconducting polymers with different spin ground states. We show that polymer building blocks with small singlet-triplet energy gap (ΔES−T) could enable small ΔES−T gap and increase the diradical character in copolymers. We first demonstrate that the spin density and solid-state interchain interactions in the high-spin polymers are crucial for their ground states. Polymers with a triplet ground state (S = 1) could exhibit doublet (S = 1/2) behavior due to the solid-state interchain spin-spin interactions. Besides, these polymers showed outstanding charge transport properties with high hole/electron mobilities and can be both n- and p-doped with superior conductivities. Our results demonstrate a rational design approach to high-mobility semiconducting polymers with different spin ground states.

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“…This new type of electron acceptor differs from the traditional INCN-type acceptors that possess flexible σ bonds, and shows an all-fused-ring molecular framework, 59 resulting in a considerably reduced reorganization energy compared with IDIC, 60 a classical small-molecule electron acceptor, 0.16 versus 0.20 eV based on density functional theory (DFT) calculations at the B3LYP/6-31G** level. Compared with IFDM, ITYM exhibits significantly elevated highest occupied molecular orbital (HOMO) (−5.77 vs −6.49 eV) and LUMO energy levels (−3.59 vs −3.95 eV) that are suitable for the OPV application.…”

Section: Introductionmentioning

confidence: 95%

Design of All-Fused-Ring Electron Acceptors with High Thermal, Chemical, and Photochemical Stability for Organic Photovoltaics

et al. 2021

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High-performance donor-acceptor electron acceptors containing 2-(3-oxo-2,3-dihydro-1H-inden-1ylidene)malononitrile (INCN)-type terminals are labile toward photooxidation and basic conditions, and new molecular designs toward electron acceptors that can achieve both high power conversion efficiencies and high stability are urgently needed. By replacing the central benzene ring in the classical ladder-type n-type semiconductor, 2,2′-(indeno[1,2b]fluorene-6,12-diylidene)dimalononitrile, with the electron-rich 4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene, we report herein the design of 2,2′- (7,7,15,15-tetrahexyl-7,15-, a new type of all-fused-ring electron acceptor (AFRA). A threestep reaction including a key Pd-catalyzed double C-H activation/intramolecular cyclization is established for the efficient synthesis of such type of electron acceptors. ITYM is confirmed by singlecrystal X-ray analysis, which shows a planar nonacyclic structure with strong π-π stacking. Compared with the classical carbon-bridged INCN-type acceptors, ITYM exhibits extraordinary stability with very promising performance. The AFRA concept opens a new avenue toward high-efficiency and -stability organic photovoltaics (OPVs).

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Quantifying Planarity in the Design of Organic Electronic Materials

Cited by 3 publications

References 64 publications

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

HOMO–LUMO Energy-Gap Tuning of π-Conjugated Zwitterions Composed of Electron-Donating Anion and Electron-Accepting Cation

High-mobility semiconducting polymers with different spin ground states

Design of All-Fused-Ring Electron Acceptors with High Thermal, Chemical, and Photochemical Stability for Organic Photovoltaics

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