Structural and solvent modulation of symmetry-breaking charge-transfer pathways in molecular triads DOI Creative Commons
Chinju Govind, Evangelos Balanikas, Gana Sanil

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Whereas the photoinduced charge-transfer properties of electron donor-acceptor dyads are now well understood, those symmetric conjugated architectures containing several identical branches have started to be scrutinised much more recently. Here, we report on our investigation dynamics a series formally centrosymmetric triads consisting quadrupolar dihydropyrrolopyrrole core substituted with two diphenylethynyl lateral branches. Using combination time-resolved electronic and vibrational spectroscopies, show that these molecules exhibit rich excited-state dynamics, which includes three different types symmetry-breaking processes depending nature end substituents as solvent: (i) symmetry breaking within core; (ii) charge transfer from one branches; (iii) between This illustrates how molecules, including location exciton, can controlled by fine tuning structural environmental parameters.

Language: Английский

Substituent effect on the electronic and optical properties of newly designed pyrrole derivatives using density functional theory DOI Creative Commons
Mamduh J. Aljaafreh, Rageh K. Hussein

Open Physics, Journal Year: 2024, Volume and Issue: 22(1)

Published: Jan. 1, 2024

Abstract This work explores six newly designed compounds obtained by several substitutions in 2,5-di(2-thienyl) pyrrole molecule. For this series of compounds, the electronic and optical properties were investigated using density functional theory time-dependent (TD-DFT). The new characterized calculating chemical parameters that correlated with their electrical properties. lowest unoccupied molecular orbital (LUMO) highest occupied (HOMO) energies are calculated B3LYP 6-311G (d, p) basis set. most low-lying energy level LUMO was found for Perr-NO 2 , indicating its effective electron injection capabilities oxidation resistance. HOMO distributions Perr-Cl displayed a remarkable complementarity throughout each component two an intermolecular charge transfer. electrostatic potential analysis demonstrated proposed have broad distribution electrophilic nucleophilic sites, which predict high degree reactivity. at bonding anti-bonding sites title performed localization function local locator techniques. Non-covalent interaction reduced gradient approach classified all types interaction: repulsive, weak, attractive interactions within compound fragments. All exhibited robust repulsive interaction, as proved red spikes 0.038 a.u. ultraviolet/visible (UV/vis) spectrum TD-DFT CAM-B3LYP models conjunction set methanol solvent, absorption bands UV range, maximum wavelength showed red-shifted increases. These could serve base material developing selective gas sensors considerable UV/vis (180–400 nm). According to research results, good candidates use precursors polymer designs optoelectronic sensor applications due conductivity photochemical

Language: Английский

Citations

5
1,4-Dihydropyrrolo[3,2-b]Pyrroles Containing New A-D-A System: Synthesis and Investigation of Their Photophysical Properties DOI Creative Commons
Güler Yagiz Erdemir

Journal of Fluorescence, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Abstract Herein, new tetraarylpyrrolo[3,2-b]pyrroles (TAPP) containing different substituents ( 4a-c , 5a-c ) on the N -phenyl rings were synthesized in high yields using a one-pot method. The 3,6 positions of pyrrolopyrol ring compound formylated by Vilsmeier-Haack reaction to synthesize acceptor-donor-acceptor (A-D-A) system ). photophysical properties all obtained derivatives investigated solvents. According results obtained, absorptions recorded around 400 nm and their emission intensities appeared 450 nm. absorption 4b 5b as 350 nm, respectively, while observed 455 440. In A-D-A formed result bonding electron-withdrawing formyl groups at position TAPP structure, Stokes shift occurred, 50 hypsochromic shifts its absorption.

Language: Английский

Citations

0
Diversifying peripheral aromatic units of pyrrolo[3,2-b]pyrrole-containing conjugated polymers and the resulting optoelectronic properties DOI
Graham S. Collier,

Julien T. Layton,

Perry Skiouris

et al.

Journal of Materials Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Pyrrolo[3,2- b ]pyrrole represents a synthetically-simple conjugated scaffold that enables accessing polymers with tailorable properties useful for organic electronics.

Language: Английский

Citations

0
Synthesis of 1,4‐dihydropyrrolo[3,2‐b]pyrrole‐containing donor–acceptor copolymers and their optoelectronic properties DOI
Kenneth‐John J. Bell, Sina Sabury,

Vanessa Phan

et al.

Journal of Polymer Science, Journal Year: 2024, Volume and Issue: 62(13), P. 2975 - 2987

Published: April 18, 2024

Abstract Donor–acceptor (D–A)‐conjugated polymers have achieved promising performance metrics in numerous optoelectronic applications that continue to motivate studying structure–property relationships and discovering new materials. Here, the materials toolbox is expanded by synthesizing D–A copolymers where 1,4‐dihydropyrrolo[3,2‐ b ]pyrrole (DHPP) directly incorporated into main chain of for first time via direct heteroarylation polymerization. Notably, synthetic complexity DHPP‐containing coupled with thieno[3,2‐ ]pyrrole‐4,6‐dione (TPD) or 3,6‐bis(2‐thienyl)‐2,5‐dihydropyrrolo[3,4‐ c ]pyrrole‐1,4‐dione (Th 2 DPP) comonomers calculated be lower compared many common conjugated synthesized arylation. The electron‐rich nature DHPPs when TPD DPP enables properties manipulated, evident measuring distinctly different absorbance redox properties. Additionally, these demonstrate their potential organic electronic applications, such as electrochromics photovoltaics. reported DHPP‐ alt ‐Th copolymer DHPP‐based colored‐to‐transmissive electrochrome achieves power conversion efficiencies ~2.5% bulk heterojunction solar cells. Overall, accessibility DHPP monomers propensity participate robust polymerizations highlights value establishing an underutilized scaffold. These fundamental attributes serve inform advance efforts development various applications.

Language: Английский

Citations

3
Expanding Color Control of Anodically Coloring Electrochromes Based on Electron-Rich 1,4-Dihydropyrrolo[3,2-b]pyrroles DOI Creative Commons

Allison M. Hawks,

Lillian M. Daniel,

Valentino S. Sorto

et al.

ACS Applied Optical Materials, Journal Year: 2024, Volume and Issue: 2(6), P. 1235 - 1244

Published: June 12, 2024

Anodically coloring electrochromes have received attention in recent years as high-contrast alternatives to cathodically due their superior optical contrast during electrochemical switching. While current systems represent significant progress for organic electrochromics, it is necessary expand the structural diversity of these materials while simultaneously reducing hazards associated with synthetic protocols. With considerations mind, a family 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) chromophores varying functionalities along 2,5-axis was envisioned accomplish goals. After predicting different absorbance traits oxidized molecules time-dependent density functional theory, DHPP peripheral were synthesized single aerobic step via an iron-catalyzed multicomponent reaction and characterized chromophores. In solution, absorb ultraviolet region electromagnetic spectrum, resulting color-neutral L*a*b* color coordinates ∼100, 0, 0. Upon chemical oxidation, each molecule transitions at various points across visible spectrum based on extent electron-donating ability can display five distinct colors. Importantly, are redox-active switching capabilities applied potential. conjunction building fundamental insights into molecular design chromophores, results simplicity DHPPs make them compelling color-controlled electrochromes.

Language: Английский

Citations

2
Synthesis of 1,2,5-substituted pyrrole derivatives by a modification of the Reisch-Schulte reaction DOI
Marco A. Almaraz-Girón, Carla Aguilar‐Lugo, Giovanna Angélica Vázquez-Hernández

et al.

Journal of Molecular Structure, Journal Year: 2023, Volume and Issue: 1300, P. 137232 - 137232

Published: Dec. 5, 2023

Language: Английский

Citations

3
Structural and solvent modulation of symmetry-breaking charge-transfer pathways in molecular triads DOI Creative Commons
Chinju Govind, Evangelos Balanikas, Gana Sanil

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Whereas the photoinduced charge-transfer properties of electron donor-acceptor dyads are now well understood, those symmetric conjugated architectures containing several identical branches have started to be scrutinised much more recently. Here, we report on our investigation dynamics a series formally centrosymmetric triads consisting quadrupolar dihydropyrrolopyrrole core substituted with two diphenylethynyl lateral branches. Using combination time-resolved electronic and vibrational spectroscopies, show that these molecules exhibit rich excited-state dynamics, which includes three different types symmetry-breaking processes depending nature end substituents as solvent: (i) symmetry breaking within core; (ii) charge transfer from one branches; (iii) between This illustrates how molecules, including location exciton, can controlled by fine tuning structural environmental parameters.

Language: Английский

Citations

0