CRYSTENGCOMM
·
2024
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IF 2.6
Wenxiu Yao,Pengfei Wu,Yidan Xie,Xinyu Shen,Shuwei Xia,Liangmin Yu
A series of charge transfer cocrystals with fluorescent properties involving 1,2,4,5-tetracyanobenzene (TCNB, C10H2N4) as the acceptor, fluorene (FR, C13H10) and its bromide 2-bromofluorene (2-BrFR, C13H9Br), carbazole (CZ, C12H9N) and its bromide 2-bromocarbazole (2-BrCZ, C12H8BrN) as donors were synthesized via cocrystal design strategies. The formation mechanism of the crystal structure was explored by density functional theory at molecular level. The stacking structure of the cocrystal was formed by the combined interaction of charge transfer interactions, π-π interactions and hydrogen bonding. N atom of donors in TCNB-CZ and TCNB-2-BrCZ could enhance the charge transfer, appear as a red shift of the fluorescence emission wavelength. Conversely, Br atom in TCNB-2-BrFR and TCNB-2-BrCZ weaken the charge transfer, giving a blue shift in fluorescence emission spectrum. The four new cocrystals exhibit tunable luminescence from green (529 nm) to yellow (552 nm) and to red (604 nm and 614 nm). It was found that the introduction of N and Br atoms in the assembly units can not only regulate the luminescence range of the cocrystals, but also adjust the luminescence efficiency, which provides a strategy for the development of promising organic luminescent materials.
研究领域:
材料科学
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有机化学
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光化学
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晶体工程
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DOI
高影响因子
Matter
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2025
·
IF 17.5
Wanjie Bai,Haotian Li,Huijie Liu,Xianheng Wang,Zhipeng Gu,Ye Yang,Yiwen Li
Black color is the most typical feature of natural and synthetic melanins, which results from the complex packing and chemical disorder of the molecular structure within melanins. From nature and beyond nature, breaking through the black color boundary, expanding the scope of inherent functions, and establishing clearer structure-function relationship of melanin is necessary but hard due to the inherent chaos structure caused by random covalent coupling and supramolecular assembly. Herein, starting from melanin-inspired monomers, we chose and assembled typical organic acceptor molecules (TCNB/TCNQ) with melanin-inspired donor molecules to prepare a series of colorful melanin-inspired pigments through the co-crystallization strategy. The resulting colorful melanin-inspired pigments exhibited multiple colors and different rod-like morphologies compared with many melanin-like polymers. Particularly, green DHI/TCNQ powder presented excellent photothermal efficiency (∼69.8%) for antibacterial application. This work would provide new structure-function tailoring strategy toward the design of melanin-like polymers with highly ordered structures and desirable properties.
研究领域:
材料科学
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有机化学
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光热治疗
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高分子化学
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超分子化学
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DOI
高影响因子
CRYSTAL GROWTH & DESIGN
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2025
·
IF 3.4
Lei Gao,Jin-Qing Li,Hui-Jun Chen,Xian-Ying Xie,Yan Liu,Xian-Rui Zhang
This study uncovers the molecular mechanism of water-triggered reversible fluorescence switching through cocrystalline assemblies of 2-methylbenzimidazole and 1,2,4,5-tetracyanobenzene. Single-crystal analysis reveals that in the hydrated phase (2METC-2), water molecules bridge donor–acceptor units via O–H···N/N–H···O hydrogen bonds, inducing substantial molecular distortion (dihedral angle change Δθ = 50.67°) and π–π compression (interplanar spacing reduction Δd = 0.209 Å). These structural rearrangements enhance exciton coupling and activate nonradiative decay pathways, quenching the fluorescence quantum yield from 13.70% (anhydrous phase, 2METC-1) to 0.48%. Variable-temperature PXRD, DSC, TGA, and cycling experiments confirm >5 reversible transitions at 80 °C/solvent with <8% intensity decay, demonstrating exceptional thermal-humidity dual responsiveness. Theoretical analyses establish that methyl-directed steric effects and cooperative C–H···O interactions construct dynamic hydrogen-bonding networks, providing an alternative strategy to conventional hydrophilic group dependency. This work establishes a new design paradigm for highly stable stimuli-responsive luminescent materials.
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高影响因子
Advanced Optical Materials
·
2023
·Vol. 11
·期 13
·2203087
·
IF 9
Shuang Ma,Hua Sun,Jinqiu Chen,Yue Yu,Haolin Lu,Shuai Wang,Jing Zhang,Jianfeng Zhao,Guankui Long,Xue-Dong Wang
In this paper, three new donor–acceptor complex forms (zBC) containing a helical-shape dibenzocarbazole analog (DBCz) as the electron donor and 1,2,4,5-tetracyanobenzene (TCNB) as the electron acceptor via a simple solution-processing strategy are reported. The beginning components self-assembled into supramolecular frameworks with glamorous alignment modes and different molar ratios: ≈1:1 P or M-enantiomer for α-cocrystal, alternated P/M-column stacking in mesmeric 2:3 β-cocrystal, and segregated stacking of γ-cocrystal. As a result, α-cocrystal exhibits bright solid-state red fluorescent, β-cocrystal shows significant optical waveguide behavior with a low optical loss coefficient of ≈0.018 dB µm −1 , and no visual light emission is observed for γ-cocrystal under ultraviolet radiation. Interestingly, the α-zBC crystal is not only emissive but also chiroptically active with dissymmetry factor ( g lum ) of 0.004. This study on chiral stacking tailoring paves a way for functional design of organic charge-transfer complex toward application in high-performance organic optoelectronics.
研究领域:
有机化学
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材料科学
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光电子学
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DOI
高影响因子
ACS Omega
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2019
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IF 2.584
Jing Wang,Aisen Li,Shuping Xu,Chongping Song,Yijia Geng,Ling Ye,Houyu Zhang,Weiqing Xu
The mixed π–π packing of the donor (D) and acceptor (A) molecules is the highlighting feature of the intermolecular interactions following charge transfer (CT) issues in organic cocrystal systems. There is an inverse relationship between the D–A interplanar distance and the intermolecular CT interaction. However, the D–A C–C surface close contact (relative areas) on the intermolecular CT interactions in organic cocrystal systems is rarely investigated. Herein, we designed and constructed a novel cocrystal and its solvate cocrystal. The structural and electrostatic potential analyses suggest that the solvation destroys the N–H···N hydrogen bond interaction between phenothiazine (PTZ) and 1,2,4,5-tetracyanobenzene (TCNB), which causes the TCNB molecules to have a 90° rotation along the normal axis of the PTZ plane. Thus, the D–A C–C surface close contact is enlarged, strengthening the intermolecular π–π stacking interactions and intermolecular CT interaction between PTZ and TCNB, which are further evidenced by the absorption and Raman spectroscopic analyses. This study provides rare evidence of the enlarged C–C surface close contact in the mixed packing between D and A that greatly contributes to the intermolecular CT interaction in a D–A cocrystal system. It also provides a deeper understanding of the role of solvation in the structure–property relationship of organic cocrystal materials.
研究领域:
材料科学
·
物理化学
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DOI
PubMed
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2026
·
IF 3.2
Jinxing Xu,Zhouyu Jiang,Mingliang Wang
A CT cocrystal FPTC of donor FPHD and acceptor TCNB was formed via self-assembly. • Donor-acceptor stacking mode and π⋯π interactions were quantified by SCXRD. • CT effect was analyzed through detailed DFT calculation. • Band-gap and optical modulation were induced by CT via the incorporation of TCNB. Investigation of the structure and optical property of charge transfer (CT) cocrystals comprising electron donors and acceptors is indispensable to clarify intrinsic relationships between donors and acceptors and construct new organic fluorescent materials. Herein, the electron donor ( E )-N’-(9-phenanthrylmethylene) benzohydrazide (FPHD), and acceptor 1,2,4,5-benzenetetracarbonitrile (TCNB) formed cocrystal FPTC (FPHD-TCNB) through supramolecular self-assembly. The crystal structure and π⋯π stacking mode of cocrystal FPTC were identified through single-crystal X-ray diffraction. The variation of C ≡ N stretch wavenumbers of TCNB and FPTC in Fourier-transform infrared spectra and the 75 nm red-shift in solid-state ultraviolet visible diffuse reflectance spectra confirmed the formation of cocrystal FPTC. Additionally, the 119 nm red-shift in solid-state fluorescence emission spectra indicated enhanced fluorescence, prolonged average fluorescence lifetime and elevated quantum yield of cocrystal FPTC. Through density functional theory (DFT), the weak interactions in cocrystal FPTC were analyzed, confirming the CT effect in FPTC. Furthermore, the narrowed band gap due to CT effect resulted in the change of transition dipole moment under excited state in cocrystal FPTC, directly leading to improved optical property of FPTC. This study illustrated CT effect on the structure and optical property of cocrystal FPTC via experimental exploration and theoretical analysis, providing a new strategy for novel organic fluorescent materials and endowing the cocrystal with promising research value for optoelectronic applications. Download: Download high-res image (235KB) Download: Download full-size image
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高影响因子
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