CRYSTAL GROWTH & DESIGN
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2024
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IF 3.2
Jinjia Guo,Lei Xu,Mingjie Cai,Zhongxin Dong,Qiong Mu,Xiaoming Wang,Haibo Fan,Feng Teng,Xuexia He,Hui Jiang,Peng Hu
Organic charge-transfer cocrystals are composed of an electron-rich donor molecule and an electron-deficient acceptor molecule, which are bonded together by intermolecular noncovalent interactions such as π–π interactions, hydrogen bonds, halogen bonds, and charge-transfer interactions. These noncovalent interactions influence the cocrystal packing structures and the photoluminescence properties. Herein, four charge transfer cocrystals, pyrene-tetrafluorophthalic anhydride (TFPA), perylene-TFPA, pyrene-tetrachlorophthalic anhydride (TCPA), and perylene-TCPA, were grown by the slow cooling method and the influence of intermolecular noncovalent interactions on the photoluminescence properties were investigated. Cocrystals of pyrene-TFPA and pyrene-TCPA exhibit a yellow rod-like morphology, while both perylene-TFPA and perylene-TCPA exhibit red rod-like shapes. Results indicate that the C–H···X (X = F, Cl, or O) interactions, π–π interactions, and charge-transfer interactions are dramatically affected by the energy difference between the HOMO of the donor and the LUMO of the acceptor. Meanwhile, for the same acceptor molecules, the positions of the photoluminescence peaks of the cocrystals red-shifted with the enhancement of weak noncovalent interactions, which paved the way to tuning the optical properties of charge transfer cocrystals.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
Computational and Theoretical Chemistry
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2025
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IF 2.8
Wenhao Su,Zhouyu Jiang,Arshad Khan,Rabia Usman,Mingliang Wang
The charge transfer (CT) cocrystal A4BTC of anthracene chalcone compound (α Z )-α-(9-Anthracenylmethylene)-4-pyridineacetonitrile (A4BCN) with 1,2,4,5-Benzenetetracarbonitrile (TCNB) was successfully constructed by supramolecular self-assembly technology. The cocrystal was formed based on π … π interactions in the D … A … D mode was stacked in the solid state. The A4BCN acted as a donor (D) and the electron-deficient TCNB acted as an acceptor (A). The pure phase formation of the cocrystal was confirmed by PXRD and FT-IR analysis. Solid-state optical properties revealed that, in comparison with the donor, A4BTC exhibited a red-shifted UV absorption band of 75 nm and a 73 nm red-shifted fluorescence emission peak. Moreover, the emission quantum yield and fluorescence lifetime showed a remarkable increase. Specifically, the quantum yield was enhanced by a factor of 4.47, and the fluorescence lifetime was extended by 6.9 ns, significantly improving the fluorescence performance. Using Density Functional Theory, the weak intermolecular and π … π interactions in A4BTC were analyzed based on the obtained SXRD crystal data, confirming the CT effect. It could also be inferred that the narrowing of the cocrystal's bandgap due to the CT effect induced a change in the transition dipole moment of the excited state. The change in the excited state dipole moment was directly correlated with the optical properties, thereby achieving the modulation of the optical properties. This study integrated theoretical calculations and experimental investigations, not only clarifying the mechanism by which π … π stacking-mediated CT effect modulates optical properties, but also establishing a theoretical model for the development of high-performance tunable organic fluorescent materials.
研究领域:
材料科学
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物理化学
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有机电子学
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理论化学
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晶体工程
✓ 已验证
产品关联
DOI
高影响因子
Computational and Theoretical Chemistry
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2025
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IF 2.8
Xianliang Gong,Yue Zhang,Zhouyu Jiang,Cunbin Du,Arshad Khan,Rabia Usman
Charge transfer (CT) cocrystals formed via non-covalent interactions play a pivotal role in governing their optical behaviors. A CT cocrystals were synthesized using 1,2,4,5-tetracyanobenzene (TCNB) as the electron acceptor and chalcone (E)-3-(anthracen-9-yl)-1-(pyridin-3-yl)prop-2-en-1-one (A3BPO) as the electron donor. Structural analysis through single-crystal X-ray diffraction (SC-XRD) unveiled that this cocrystal predominantly comprise a mixed stacking arrangement guided by face-to-face π···π interactions, with the overall stability of CT cocrystal stacking bolstered by auxiliary hydrogen bonds. The relationship between structure and properties was scrutinized using various analytical techniques including Powder X-ray diffraction (PXRD), FT-IR, UV–visible absorption, and fluorescence spectroscopy. Density functional theory (DFT) simulations elucidated that the modified optical properties primarily stem from CT between acceptor and donor. These findings contribute significantly to a clearer understanding of how stacking modes in CT cocrystals influence the interplay between CT and optical properties.
研究领域:
材料科学
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物理化学
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晶体工程
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光学材料
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理论化学
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有机电子学
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产品关联
DOI
高影响因子
CRYSTENGCOMM
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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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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
You-Zhou Yang,Yun Rong,Yuan-Yuan Li,Mengmeng Ma,Dan Chen,Hang Lu,Chang Wu,Boyuan Shen,Jin-Ping Guan,Ming-Peng Zhuo
Smart materials demonstrate fascinating responses to environmental physical/chemical stimuli, including thermal, photonic, electronic, humidity, or magnetic stimuli, which have attracted intensive interest in material chemistry. However, their limited/harsh stimuli-responsive behavior or sophisticated postprocessing leads to enormous challenges for practical applications. Herein, we rationally designed and synthesized thermochromic Ni(II) organometallic [(C2H5)2NH2]2NiCl4–xBrx via a facile mechanochemical strategy, which demonstrated a reversible switch from yellow to blue color with a tunable phase-transition temperature from 75.6 to 61.7 °C. The simple electrospinning technology was applied to fabricate thermochromic Ni(II) organometallic-based nanofiber membranes for temperature monitoring. Furthermore, the organic charge-transfer cocrystal with a wide spectral absorption of 300–1950 nm and a high-efficiency photothermal conversion was combined with thermochromic Ni(II) organometallics for the desired dual-stimuli photo/thermochromism. This work supplies a new strategy for realizing multiple stimuli-responsive applications, such as thermal/light sensor displays and information storage.
研究领域:
材料化学
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智能材料
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热致变色材料
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光致变色材料
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纳米技术
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传感器
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产品关联
DOI
PubMed
高影响因子
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