Chiral Supramolecular Polymers Assembled from Conformationally Flexible Amino‐Acid‐Substituted Biphenyldiimides DOI
Grzegorz Markiewicz,

Adrianna Szmulewicz,

Łukasz Majchrzycki

et al.

Macromolecular Rapid Communications, Journal Year: 2022, Volume and Issue: 44(5)

Published: Nov. 17, 2022

Hydrogen-bonded polymers are a class of highly dynamic supramolecular aggregates, whose self-assembly may be tuned by very mild external or internal stimuli. However, the rational design chiral supramolecules remains challenging especially when flexible components involved. The combination inherent weakness and nature intermolecular bonds that hold together such assemblies with unrestricted molecular motions introduces additional factors which affect process. In this report, four amino acid-derived biphenyldiimides into open-chain 1D is presented. While primary driving force, COOH···HOOC hydrogen bonding, responsible for polymer growth in all cases, acid side chains play an important role either stabilizing destabilizing obtained, as deduced from studies thermodynamics Furthermore, substantial differences structural governing polymerization process between liquid static solid found. This work demonstrates potential rather unexplored diimide-based organic dyes formation well-organized tunable properties.

Language: Английский

Chirality of Perylene Diimides: Design Strategies and Applications DOI
Jie Li, Pengyu Li, Mingyu Fan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)

Published: March 31, 2022

Abstract Chirality is a particularly important concept in nature and exists at all length scales, ranging from the molecular level to supramolecular level. Over last two decades, various design strategies have been developed construct chiral materials based on perylene diimides (PDIs) mimic assembly process biological systems, but applications of these aggregates are still an early stage. This Minireview summarizes recent progress synthesis properties PDIs. The chirality PDI‐based can be generated by three different approaches: twisted planes PDIs, substituents co‐assembly achiral PDIs guests. A comprehensive understanding as well potential future developments also provided.

Language: Английский

Citations

65
New advances in chiral nanographene chemistry DOI Creative Commons
Hannah V. Anderson, Nicolai D. Gois, Wesley A. Chalifoux

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(16), P. 4167 - 4197

Published: Jan. 1, 2023

This review will highlight several recent and lesser-reviewed works related to the preparation of chiral nanographenes, specifically focusing on structures prepared by non-Scholl methods.

Language: Английский

Citations

37
A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence DOI Creative Commons
Samuel E. Penty, Georgia R. F. Orton, Dominic J. Black

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5470 - 5479

Published: Feb. 14, 2024

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized framework is conducive to directing π–π self-assembly and delivering strong persistent CPL signal. Here, perylene diimides (PDIs) an excellent choice dye component because, alongside their tunable photophysical properties, functionalization PDI's core yields twisted, π-system, capable CPL. However, configurationally stable PDI-based macrocycles rare, those that also beyond dimers unprecedented, both which advantageous robust self-assembled chiroptical materials. In this work, we report first bay-connected bis-PDI macrocycle (ΔG⧧ > 155 kJ mol–1). We use chirally locked uncover new knowledge PDI perform quantitative imaging resulting single-crystal As such, discover chirality 1,7-disubstituted provides rational route designing H-, J- concomitant H- J-type important arrangements optimizing (chir)optical charge/energy transport properties. Indeed, reveal amplified in single crystals our by quantifying degree emitted light circular polarization from such materials time using CPL-Laser Scanning Confocal Microscopy.

Language: Английский

Citations

15
Helically Twisted Nanoribbons Based on Emissive Near-Infrared Responsive Quaterrylene Bisimides DOI

Bernhard Mahlmeister,

Magnus Mahl,

Helmut Reichelt

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(23), P. 10507 - 10514

Published: June 1, 2022

Graphene nanoribbons (GNRs) have the potential for next-generation functional devices. So far, GNRs with defined stereochemistry are rarely reported in literature and their optical response is usually bound to ultraviolet or visible spectral region, while covering near-infrared (NIR) regime still challenging. Herein, we report two novel quaterrylene bisimides either one- twofold-twisted π-backbones enabled by steric congestion of a fourfold bay arylation leading an end-to-end twist up 76°. The strong interlocking effect π-stacked aryl substituents introduces rigidification chromophore unambiguously proven single-crystal X-ray analysis. This leads unexpectedly NIR emissions at 862 903 nm quantum yields 1.5 0.9%, respectively, further ensuring high solubility as well resolvable highly stable atropo-enantiomers. Circular dichroism spectroscopy these enantiopure chiral compounds reveals Cotton Δε 67 M-1 cm-1 centered far region 849 nm.

Language: Английский

Citations

32
Enantiopure J-Aggregate of Quaterrylene Bisimides for Strong Chiroptical NIR-Response DOI

Bernhard Mahlmeister,

Tim Schembri,

Vladimir Stepanenko

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13302 - 13311

Published: June 7, 2023

Chiral polycyclic aromatic hydrocarbons can be tailored for next-generation photonic materials by carefully designing their molecular as well supramolecular architectures. Hence, excitonic coupling boost the chiroptical response in extended aggregates but is still challenging to achieve pure self-assembly. Whereas most reports on these potential cover UV and visible spectral range, systems near infrared (NIR) are underdeveloped. We report a new quaterrylene bisimide derivative with conformationally stable twisted π-backbone enabled sterical congestion of fourfold bay-arylation. Rendering π-subplanes accessible small imide substituents allows slip-stacked chiral arrangement kinetic self-assembly low polarity solvents. The dispersed solid-state aggregate reveals sharp optical signature strong J-type both absorption (897 nm) emission (912 far NIR region reaches dissymmetry factors up 1.1 × 10-2. structural elucidation was achieved atomic force microscopy single-crystal X-ray analysis which we combined derive model stranded enantiopure superhelix. could deduce that role phenyl not only granting axial chirality also guiding chromophore into needed chirality.

Language: Английский

Citations

13
Chirality of Perylene Diimides: Design Strategies and Applications DOI
Jie Li, Pengyu Li, Mingyu Fan

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(27)

Published: March 31, 2022

Abstract Chirality is a particularly important concept in nature and exists at all length scales, ranging from the molecular level to supramolecular level. Over last two decades, various design strategies have been developed construct chiral materials based on perylene diimides (PDIs) mimic assembly process biological systems, but applications of these aggregates are still an early stage. This Minireview summarizes recent progress synthesis properties PDIs. The chirality PDI‐based can be generated by three different approaches: twisted planes PDIs, substituents co‐assembly achiral PDIs guests. A comprehensive understanding as well potential future developments also provided.

Language: Английский

Citations

16
Progress of Monomeric Perylene Diimide Derivatives As Non-Fullerene Acceptors for Organic Solar Cells DOI
Linhua Zhang, Zhili Chen,

Fengbo Sun

et al.

Journal of Electronic Materials, Journal Year: 2022, Volume and Issue: 51(8), P. 4224 - 4237

Published: June 14, 2022

Language: Английский

Citations

16
Nonfused Dimethoxybenzene Electron Acceptors in Organic Solar Cells: From Molecular Design to Structure–Performance Relationship DOI

Zifu Zang,

Ying Yu, Peng Song

et al.

The Journal of Physical Chemistry C, Journal Year: 2022, Volume and Issue: 127(1), P. 110 - 124

Published: Dec. 28, 2022

The photovoltaic mechanism of asymmetric non-fullerene acceptors (NFAs) has not been sufficiently understood, although it is developing as a forceful method to design effective organic solar cells. This article systematically investigated and designed several configurations nonfused at the micro level. Skeletons were constructed by central 1,4-dimethoxybenzene core flanked different dithieno-pyrroles thiophene derivates electron-donating groups; end-capped groups composed two 1,1-dicyanomethyl-3-indanone. Through theoretical calculation, one found that DBPT series possessed narrower gaps, broadened absorption near-infrared region, larger electron-accepting power, separated distance holes electrons. They also yielded enhancement mobility, which may relate significant dipole moment electronic coupling. Furthermore, we device models using PBDB-T donor. heterojunction model results show optimized blends PBDB-T/DBPT-4F achieved more intermolecular fragment charge amounts, CT states, smaller binding energy, showing separation/recombination ratio. Then, under macro-scale model, better power conversion efficiency 14.69%, owing large simulated JSC 18.82 mA cm–2, consistent with trend interfacial transfer property. work provided global description molecular light response microscopic physicochemical process, sheds on structure–property relationship unfused NFAs enables strategy develop valuable OSCs.

Language: Английский

Citations

15
Synthesis and Properties of Achiral and Chiral Dipyrenoheteroles and Related Compounds DOI

Ryan J. Malone,

Jonas Spengler,

Rachael A. Carmichael

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 226 - 230

Published: Jan. 3, 2023

Achiral and chiral isomers of dipyrenoheteroles were synthesized via alkyne benzannulation. The electronic properties these compounds examined using cyclic voltammetry differential pulse voltammetry. enantiomers the separated, their optical in circular dichroism circularly polarized luminescence studies. exhibited a large bathochromic shift, relative to achiral isomer, both absorbance fluorescence, resulting from decreased symmetry, rather than change size backbone.

Language: Английский

Citations

9
Direct Observation of Ultrafast Relaxation Dynamics of a Mixed Excimer State in Perylene Monoimide Dimer by Femtosecond Transient Absorption DOI
Chaochao Qin,

Zheng Zhang,

Qiaoling Xu

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(10), P. 2455 - 2462

Published: March 3, 2023

A J-type dimer PMI-2, two perylene monoimides linked by butadiynylene bridger was prepared, and its excited-state dynamics studied using ultrafast femtosecond transient absorption spectroscopy, along with steady-state spectroscopy quantum chemical calculations. It is evidently demonstrated that the symmetry-breaking charge separation (SB-CS) process in PMI-2 positively mediated an excimer, which mixed localized Frenkel excitation (LE) interunit transfer (CT) state. Kinetic studies show that, polarity increasing of solvent, transformation excimer from a mixture to CT state accelerated, recombination time reduced obviously. Theoretical calculations indicate these are due obtaining more negative free energy (ΔGcs) lower levels highly polar solvents. Our work suggests can be formed suitable structure, sensitive solvent environment.

Language: Английский

Citations

9