Organic Donor‐Acceptor Systems for Photocatalysis

Advanced Science, Год журнала: 2023, Номер 11(10)

Опубликована: Дек. 25, 2023

Abstract Organic semiconductor materials are considered to be promising photocatalysts due their excellent light absorption by chromophores, easy molecular structure tuning, and solution‐processable properties. In particular, donor‐acceptor (D‐A) type organic photocatalytic synthesized introducing D A units intra‐ or intermolecularly, have made great progress in studies. More more studies demonstrated that the D‐A combine effective carrier separation, tunable bandgap, sensitive optoelectronic response, an strategy for enhancing absorption, improving exciton dissociation, optimizing transport. This review provides a thorough overview of strategies aimed at performance semiconductors. Initially, essential methods modifying materials, such as interface engineering, crystal interaction modulation, briefly discussed. Subsequently, delves into various based on intramolecular intermolecular interactions, encompassing small molecules, conjugated polymers, crystalline supramolecules, heterojunctions. Meanwhile, energy band structures, dynamics, redox‐active sites under different bonding modes Finally, highlights advanced applications photocatalystsand outlines prospective challenges opportunities.

Язык: Английский

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Bifurcated Polymorphic Transition and Thermochromic Fluorescence of a Molecular Crystal Involving Three-Dimensional Supramolecular Gear Rotation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8131 - 8141

Опубликована: Март 12, 2024

The ability of molecules to move and rearrange in the solid state accounts for polymorphic transition stimuli-responsive properties molecular crystals. However, how crystal structure determines motion remains poorly understood. Here, we report that a three-dimensional (3D) supramolecular gear network green-emissive polymorph 1G dialkylamino-substituted anthracene-pentiptycene π-system (1) enables an unusual bifurcated into yellow-emissive (1Y) new (1G*) via 3D correlated rotation. 90° forward rotation causes conformation between octyl anthracene units change from syn anti, ladder-like columns constrict, disengage. This cooperative is marked by gradual formation intermediate (1I) across entire 170 230 °C, which then undergoes (forward or backward rotation) irreversible transitions form polymorphs 1Y 1G* at 230–235 °C. Notably, similar but lacks engagement, preventing its transformation 1Y. Nevertheless, can be restored grinding fuming with dichloromethane (DCM) vapor. work illustrates correlation solid-state behavior demonstrates system efficiently transmits thermal energy drive induce fluorochromism through significant conformational packing changes.

Язык: Английский

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Tris-Azo Triangular Paraphenylenes: Synthesis and Reversible Interconversion into Radial π-Conjugated Macrocycles

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10246 - 10250

Опубликована: Апрель 3, 2024

We report the synthesis of cycloparaphenylene derivatives featuring tris-azo groups. The smaller derivative, [3]cycloazobenzene, adopts a triangular all-cis form and exhibits thermally photochemically stable characteristics due to significant ring strain as well symmetric Kagome-patterned crystal packing. In contrast, as-synthesized [3]cycloazobenzene with three biphenylene bridges form, which undergoes photoinduced isomerization, leading photostationary state. Interestingly, addition an excess acid selectively leads formation all-trans form. DFT calculations reveal that interconversion from circular shape correlates increase in HOMO decrease LUMO, intrinsic radial π-conjugated systems.

Язык: Английский

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Crystal Structure and Phase Transitions of a Novel Crown Ether Clathrate [(2-Thienylmethylamine)(18-crown-6)]2[Cd2Cl6]

Russian Journal of Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

Язык: Английский

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Solution State‐Like Reactivity of a Flexible Crystalline Werner‐Type Metal Complex

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 2, 2024

Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist developing that have similar degrees of flexibility as solution. Herein, we report the preparation new flexible metal complex [Cd(CF

Язык: Английский

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Synthesis, characterization of a dual-stimuli-responsive cobalt(III) complex: comparison of photo/thermo mechanical behaviour in crystal and polymer composite

CrystEngComm, Год журнала: 2024, Номер 26(36), С. 5004 - 5012

Опубликована: Янв. 1, 2024

A nitropentaammine cobalt( iii ) complex shows dual-stimuli-mecahnical behaviour under both UV light and heat. The photo/thermo-mechanical of the was successfully transferred to a polymer composite showing actuating behaviour.

Язык: Английский

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Modulating the isomerization of bpp-modified azoheteroarene by transition metal ions coordination

Inorganic Chemistry Communications, Год журнала: 2024, Номер 168, С. 112986 - 112986

Опубликована: Авг. 15, 2024

Язык: Английский

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Polymorph Driven Diversification of Photosalient Responses in a Zinc(II) Coordination Complex

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Diversification of the photosalient effect among polymorphs a Zn( ii ) coordination complex is reported.

Язык: Английский

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Solution State‐Like Reactivity of a Flexible Crystalline Werner‐Type Metal Complex

Angewandte Chemie, Год журнала: 2024, Номер 136(42)

Опубликована: Авг. 2, 2024

Abstract Flexible crystalline solids exhibit unique properties in response to external stimuli like heat and light. However, challenges exist developing that have similar degrees of flexibility as solution. Herein, we report the preparation new flexible metal complex [Cd(CF 3 SO ) 2 (4‐spy) 4 ] (4‐spy=4‐styrylpyridine), which contains photoreactive 4‐spy ligand. Unlike traditional solids, this displays solution state‐like [2+2] photocycloaddition reactivity. Specifically, UV irradiation material leads formation same diverse array dimers cis isomer are generated by photoreaction state. In addition, photoresponsive solid a photosalient effect photo‐induced pores. The origin photoreactivity is related Cd(II) cation fluorinated CF anion, multi‐orientational arrangement ligands.

Язык: Английский

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Reversible Sliding Motion by Hole‐Injection in Ammonium‐Linked Ferrocene, Electronically Decoupled from Noble Metal Substrate by Crown‐Ether Template Layer

Small, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 30, 2024

Abstract Artificial molecular machines, especially when based on wheel‐and‐axle complexes, can generate mechanical motions in response to external stimuli. Ferrocene (Fc) is a key component, but it decomposes at 300 K metal surfaces. Here, novel method presented construct and control the complex composed of ammonium‐linked ferrocene (Fc‐amm) tetrabrominated crown ether (BrCR) Cu(111) surface. Fc‐amm molecules are periodically arranged BrCR monolayer film imaged using scanning tunneling microscopy spectroscopy. A lateral motion Fc groups by ≈0.1 nm observed for pairs “edge‐on” upon hole injection. This sliding reversible controlled applied voltage. Theoretical analysis indicates that caused increased Coulomb repulsion hole‐doped Fc‐amm+ ions accompanied weakening CH‐π interactions. These findings open new avenues developing nanomolecular devices on‐surface bottom‐up processes.

Язык: Английский

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