Supramolecularly Engineered J-Aggregates Based on Perylene Bisimide Dyes

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 54(3), P. 642 - 653

Published: Dec. 8, 2020

The discovery of the self-assembly cyanine dyes into J-aggregates had a major impact on development dye chemistry due to emergence new useful properties in aggregated state. unique optical features these are narrowed, bathochromically shifted absorption bands with almost resonant fluorescence an increased radiative rate that results from coherently coupled molecular transition dipoles arranged slip-stacked fashion. Because their desirable properties, gained popularity field functional materials and enabled efficient photosensitization silver halide grains color photography. However, despite good theoretical understanding structure-property relationships by exciton model, further examples remained scarce for long time as supramolecular designs guide formation aggregates required arrangement were lacking.Drawing inspiration bacteriochlorophyll c self-organization found chlorosomal light-harvesting antennas green sulfur bacteria, we envisioned use nature's blueprint develop perylene bisimides (PBIs). This class is applied high-performance pigments n-type organic semiconductors transistors solar cells. Combining outstanding photochemical thermal stability, high tinctorial strength excellent fluorescence, PBIs therefore ideal model system preparation wide range potential applications.In this Account, elucidate how combination steric constraints hydrogen bonding receptor sites can PBI packing motifs J-type coupling. We will discuss polymerization multiple hydrogen-bonded strands aqueous media minor structural modifications monomeric molecules be used obtain near-infrared absorbing J-aggregates, organogels, or thermoresponsive hydrogels. Pushing boundaries bulk, engineering substituents' requirements dendron-wedge approach afforded adjustable numbers helical columnar liquid-crystalline state lamellar phases. To fully explore potential, have studied collaborative work spectroscopists, physicists, theoreticians. In way, migration over distances up 180 nm was shown, insights influence static disorder transport excitation energy derived. Furthermore, application demonstrated photonic microcavities, thin-film transistors,

Language: Английский

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π-Extended perylene diimide double-heterohelicenes as ambipolar organic semiconductors for broadband circularly polarized light detection

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 8, 2021

Abstract Despite great challenges, the development of new molecular structures with multiple and even conflicting characteristics are eagerly pursued for exploring advanced applications. To develop high-performance chiral organic semiconducting molecules, a distorted π-system is required strong coupling circularly polarized light (CPL), whereas planar π-stacking systems necessary high charge-carrier mobility. address this dilemma, in work, we introduce skeleton merging approach through distortion perylene diimide (PDI) core four fused heteroaromatics to form an ortho -π-extended PDI double-[7]heterohelicene. double helicene inherits dissymmetry factor from skeleton, extended π-planar system concurrently maintains level charge transport properties. In addition, -π-extension brings about near-infrared (NIR) absorption ambipolar abilities, endowing corresponding phototransistors photoresponsivity 450 120 mA W −1 p - n -type modes respectively, along external quantum efficiency (89%) under NIR irradiations. Remarkably, these enable broadband CPL detections up spectral region semiconductors.

Language: Английский

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Giant Rylene Imide-Based Electron Acceptors for Organic Photovoltaics

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(4), P. 961 - 975

Published: Jan. 4, 2021

ConspectusRylene imides are oligo(peri-naphthalene)s bearing one or two six-membered carboxylic imide rings. Their flexible reaction sites and unique photoelectronic properties have afforded active research for applications in photovoltaic devices, light-emitting diodes, fluorescent sensors. Over the past few decades, synthetic flexibility along with evolution of molecular design principles novel aromatic has rendered these intriguing dyes considerably valuable, especially organic photovoltaics (OPVs).During course evolution, most difficult criterion to meet is how modulate intra- intermolecular interactions alter aggregation behavior rylene as well their compatibility donor materials, prerequisite that appropriate energy level maintained. In meantime, our group focused on precise synthesis π-extended electron acceptors (RIAs) rationally chemical electronic structure, packing arrangement, properties. These powerful strategies include construction a fully conjugated rigid multichromophoric architecture successful integration heteroatoms. Herein, oligomers precisely defined giant imides. Importantly, provide vast space progress RIAs present more comprehensive structure–performance relationship network can be distinguished from other acceptor systems. particular, acquisition fused superhelical architectures provides meaningful reference pluralistic development OPVs, such triplet solar cells polarized-light detectors. Meanwhile, introduction heteroatoms into skeleton donor/acceptor interfaces enhanced thereby suppresses polaron-pair binding energy. Nonetheless, much remains implemented broaden absorption capability realize full utilization chiral isomers wide strong UV–vis spectroscopic response.In this Account, we an overview approaches toward supermolecular framework reformed principle imide-based since 2012. We begin discussion rapidly emerging Then several typical examples remarkable working mechanisms selected, aimed at providing in-depth structure–property–performance relationships. The remaining challenges newly information further put forward. It aspiration Account will trigger intensive interest pluralist rylene-based acceptors, accelerating profound sustainable cells.

Language: Английский

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Recent developments of perylene diimide (PDI) supramolecular photocatalysts: A review

Journal of Photochemistry and Photobiology C Photochemistry Reviews, Journal Year: 2021, Volume and Issue: 48, P. 100436 - 100436

Published: June 30, 2021

Language: Английский

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Molecular Carbon Imides

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 14976 - 14991

Published: July 29, 2022

The creation and development of new forms nanocarbons have fundamentally transformed the scientific landscape in past three decades. As members nanocarbon family with accurate size, shape, edge structure, molecular carbon imides (MCIs) shown unexpected unique properties. Particularly, imide functionalization strategy has endowed these rylene-based carbons fascinating characteristics involving flexible syntheses, tailor-made structures, diverse properties, excellent processability, good stability. This Perspective elaborates design evolution to functional landscapes, illustrative examples are given, including a promising library multi-size multi-dimensional MCIs rigidly conjugated π-architectures, ranging from 1D nanoribbon 2D nanographene cross-dimensional MCIs. Although researchers achieved substantial progress using as components for exploration charge transport, photoelectric conversion, chiral luminescence performances, they far unleashing their full potential. Developing highly efficient regioselective coupling/ring-closure reactions formation multiple C–C bonds annulation electron-deficient aromatic units is crucial. Prediction by theory help machine learning artificial intelligence research along reliable nanotechnology characterization will give an impetus blossom related fields. Future investigations also advance toward─or even focus on─the emerging potential functions, especially fields electronics spin electronics, which expected open avenues.

Language: Английский

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“Spine Surgery” of Perylene Diimides with Covalent B–N Bonds toward Electron-Deficient BN-Embedded Polycyclic Aromatic Hydrocarbons

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 3091 - 3098

Published: Feb. 9, 2022

BN-embedded polycyclic aromatic hydrocarbons (PAHs) with unique optoelectronic properties are underdeveloped relative to their carbonaceous counterparts due the lack of suitable and facile synthetic methods. Moreover, dearth electron-deficient PAHs further hinders application in organic electronics. Here we present first synthesis novel perylene diimide derivatives (B2N2-PDIs) featuring n-type B-N covalent bonds. The structures these compounds fully confirmed through detailed characterizations NMR, MS, X-ray crystallography. Further investigation shows that introduction BN units significantly modifies photophysical electronic B2N2-PDIs is understood aid theoretical calculations. Compared parent diimides (PDIs), exhibit deeper highest occupied molecular orbital energy levels, new absorption peaks high-energy region, hypsochromic shift emission maxima, decrement photoluminescent quantum yields. Single-crystal field-effect transistors based on showcase an electron mobility up 0.35 cm2 V-1 s-1, demonstrating potential materials.

Language: Английский

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Anomalous deep-red luminescence of perylene black analogues with strong π-π interactions

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 6, 2023

Abstract Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π−π stacking arrangement. However, contrary to luminescent monomers, deep-red PBI pigments commonly non- or only weakly fluorescent due (multiple) quenching pathways. Here, we introduce N -alkoxybenzyl substituted PBIs that contain π arrangement (exhibiting d ≈ 3.5 Å, longitudinal transversal displacements of 3.1 Å 1.3 Å); however, they afford emitters with solid-state fluorescence quantum yields ( Φ F ) up 60%. Systematic photophysical computational studies in solution solid state reveal a sensitive interconversion PBI-centred locally excited charge transfer state, which depends dihedral angle θ between benzyl alkoxy groups. This effectively controls emission process, enables high by circumventing common pathways observed for perylene analogues.

Language: Английский

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The Importance of the Purification Step and the Characterization of the Products in the Synthesis of Carbon Nanodots

Small, Journal Year: 2023, Volume and Issue: 19(31)

Published: Feb. 20, 2023

In the synthesis of carbon nanodots (CNDs), critical step purification from starting materials and unwanted side products is faced. exciting race toward new interesting CNDs, this problem often underestimated, leading to false properties erroneous reports. fact, on many occasions, described for novel CNDs derive impurities not completely eliminated during process. Dialysis, instance, always helpful, especially if are soluble in water. Perspective, importance characterization steps, order obtain solid reports reliable procedures, emphasized.

Language: Английский

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Organic solar cells based on molecular perylene diimides-type nonfullerene acceptors: achievements, challenges and the future

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Language: Английский

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Self-Assembled Perylene Bisimide-Cored Trigonal Prism as an Electron-Deficient Host for C₆₀ and C₇₀ Driven by “Like Dissolves Like”

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15950 - 15960

Published: Aug. 26, 2020

Poor processability of fullerenes is a major remaining drawback for them to be studied monomolecularly and find real-life applications. One the strategies tackle this problem encapsulate within host, which however quite often, accompanied by significant alteration their physical/chemical properties as encountered in chemical modification. To minimize effect, an electron-deficient entities-based, dissolvable, fluorescence active supramolecular host was designed constructed via coordination-driven self-assembly o-tetrapyridyl perylene bisimide (PBI) with cis-(PEt3)2Pt(OTf)2. The trigonal prism 1 possesses trigonal-prismatic inner cavity 14.7 Å diameter its inscribed circle. Host-guest chemistry investigations revealed that both C60 C70 could quantitatively encapsulated 1:1 ratio. Further studies demonstrated produced host-guest complex 1⊃C70 significantly more stable than 1⊃C60, allowing complete transformation latter former separation from mixture C60. inclusion state rotate freely cavity. Electrochemistry spectroscopy disclosed encapsulation guests shows little effect upon reduction properties. Thus, "like dissolves like" believed main driving force formation complexes. Moreover, complexes can fabricated into monomolecular membranes using conventional Langmuir-Blodgett technique. We propose these unique used model ensembles further single molecular 2D membrane states. In addition, reversible four-electron property may allow applications photo/electrocatalysis, organic electronics, etc.

Language: Английский

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