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学者姓名：张书泉
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Abstract ：
Photochromic materials and room-temperature phosphorescence (RTP) are essential for applications in optoelectronics and bioimaging. Organic-inorganic hybrid materials, particularly those exhibiting donor-acceptor (D-A) characteristics through supramolecular interactions, have shown significant potential to integrate both photochromic and RTP properties. Among them, the anion-pi and pi-pi interactions have been extensively studied; however, the role of anion-pi-pi interactions in hybrid materials remains largely unexplored. This study investigated three naphthalenediimide-polyoxometalate (NDI-POM) hybrids: (H2DMAP-NDI)(HPW12O40)(NMP)2 (1), (HDMAP-NDI)2(HPW12O40)(NMP)2 (2), and (HDMAP-NDI)2(HPW12O40)(NMP)7 (3), focusing on the impact of anion-pi-pi interactions on their photochromic and RTP properties. The results indicate that hybrid 1 exhibits the fastest photoresponse and highest RTP quantum yield, primarily driven by anion-pi interactions. Hybrid 2, which involves anion-pi-pi interactions, shows slower photochromism and lower RTP yield due to exciton localization and nonradiative decay paths resulting from pi-pi stacking. Hybrid 3, characterized by excessively strong interactions, is unstable and nonemissive. This study provides valuable insights into the role of anion-pi-pi interactions in hybrid materials and offers a framework for designing advanced photoresponsive materials with tunable properties for diverse applications.
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| GB/T 7714 | Di, Yi-Ming , Song, Yu-Ping , Zhang, Shu-Quan et al. Anion-π(-π) Interactions in Donor-Acceptor Hybrid Materials to Control Photochromism and Room-Temperature Phosphorescence [J]. | INORGANIC CHEMISTRY , 2025 , 64 (12) : 6183-6191 . |
| MLA | Di, Yi-Ming et al. "Anion-π(-π) Interactions in Donor-Acceptor Hybrid Materials to Control Photochromism and Room-Temperature Phosphorescence" . | INORGANIC CHEMISTRY 64 . 12 (2025) : 6183-6191 . |
| APA | Di, Yi-Ming , Song, Yu-Ping , Zhang, Shu-Quan , Lin, Mei-Jin . Anion-π(-π) Interactions in Donor-Acceptor Hybrid Materials to Control Photochromism and Room-Temperature Phosphorescence . | INORGANIC CHEMISTRY , 2025 , 64 (12) , 6183-6191 . |
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Harnessing supramolecular interactions to regulate the structure and performance of functional materials is a key challenge in materials chemistry. Herein, the study utilizes 18-crown-6 (18C6) ether-assisted alkali-metal (Na, K, Cs) copper(I) iodide supramolecular assemblies to precisely regulate the material structures. This approach facilitated the transition from 1D mono-royal crown coordination (18C6@KCuI2, CKCI) to 0D di-royal crown ((18C6)(2)@Na-2(H2O)(3)Cu4I6, CNCI) and tri-royal crown ((18C6)(3)@Cs2Cu2I4, CCCI) structures. Interestingly, the CCCI single-crystal exhibits outstanding scintillation properties, with a high relative light yield of 71 000 photons MeV-1 and an ultralow detection limit of 39.3 nGy s(-1), which can be attributed to the synergistic effects of 18C6 and copper-iodide clusters. It stabilizes the self-trapped exciton state, enhances exciton localization, and reduces non-radiative losses, thus resulting in a large Stokes shift of 193 nm and near-unity photoluminescence quantum yield of 99.4%. Additionally, 18C6 can promote crystal nucleation and growth, making it easy to prepare centimeter-scale transparent single crystals with >80% transmittance, such as CCCI single crystal can achieve an ultrahigh-resolution X-ray imaging of 26.3 lp mm(-1). It demonstrates that the structure and performance of halide scintillators can be regulated through supramolecular interactions, which provides a new approach for developing high-performance scintillator materials.
Keyword ：
18-crown-6 18-crown-6 copper(I) iodide copper(I) iodide self-trapped exciton state self-trapped exciton state supramolecular scintillators supramolecular scintillators X-ray imaging X-ray imaging
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| GB/T 7714 | Ye, Yuanji , Di, Yiming , Zhou, Jiahao et al. Crown Ether-Assisted Alkali-Metal Copper(I) Iodide Supramolecular Scintillators with Near-Unity Emission for Ultrahigh-Resolution X-Ray Imaging [J]. | ADVANCED FUNCTIONAL MATERIALS , 2025 . |
| MLA | Ye, Yuanji et al. "Crown Ether-Assisted Alkali-Metal Copper(I) Iodide Supramolecular Scintillators with Near-Unity Emission for Ultrahigh-Resolution X-Ray Imaging" . | ADVANCED FUNCTIONAL MATERIALS (2025) . |
| APA | Ye, Yuanji , Di, Yiming , Zhou, Jiahao , Qiu, Qiangwen , Chen, Yuhua , Zhong, Shanyuan et al. Crown Ether-Assisted Alkali-Metal Copper(I) Iodide Supramolecular Scintillators with Near-Unity Emission for Ultrahigh-Resolution X-Ray Imaging . | ADVANCED FUNCTIONAL MATERIALS , 2025 . |
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As an emerging class of hybrid complexes, donor-acceptor (D-A) hybrid heterostructures, which combine the advantages of both organic and inorganic photoactive components, provide excellent platforms for the fabrication of photochromic materials with enhanced photo-responsive performances. Herein, four novel hybrid heterostructures, namely H3TPT(PW12O40)2NMP (1), (H1.5TPT)(2)(PW12O40) (2), (H3TPT)(2)(SiW12O40)2Cl2MeCN (3), and H3TPT(HPMo12O40)Cl3NMP (4) (TPT is tri(4-pyridyl)-s-triazine, NMP is N-methylpyrrolidone), have been synthesized and characterized. Benefitting from the strong interactions (anion-pi interactions) and matching electron energy levels between the donors and acceptors, some of them exhibited ultrafast photochromic behaviour even up to 1 second. Furthermore, based on experimental and theoretical calculations, the plausible PIET process and structure-activity relationship have been discussed in detail.
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| GB/T 7714 | Chen, Yue-Chen , Di, Yi-Ming , Zhang, Shu-Quan et al. Polyoxometalate/s-triazine hybrid heterostructures with ultrafast photochromic properties [J]. | DALTON TRANSACTIONS , 2024 , 53 (7) : 3215-3223 . |
| MLA | Chen, Yue-Chen et al. "Polyoxometalate/s-triazine hybrid heterostructures with ultrafast photochromic properties" . | DALTON TRANSACTIONS 53 . 7 (2024) : 3215-3223 . |
| APA | Chen, Yue-Chen , Di, Yi-Ming , Zhang, Shu-Quan , Lin, Mei-Jin . Polyoxometalate/s-triazine hybrid heterostructures with ultrafast photochromic properties . | DALTON TRANSACTIONS , 2024 , 53 (7) , 3215-3223 . |
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Semiconductive metal-organic frameworks (MOFs) with donor-acceptor (D-A) characteristics have garnered attractive attention due to their capacity for separating and transferring photogenerated charges, making them promising candidates for high-performance X-ray detectors. However, the low charge transfer efficiency between the metal nodes and organic ligands limits the X-ray-to-electricity conversion efficiency of these materials. Herein, an additional photoactive donor (D') is introduced by incorporating a heavy atom-containing polyoxometalate (POM) [alpha-SiW12O40](4-) into a binary {[Nibcbp(H2O)(2)](H2O)(4)Cl}(n) (Ni-bcbp, bcbp: H(2)bcbp2Cl = 1,1 '-bis(4-carboxyphenyl)(4,4 '-bipyridinium) dichloride) MOF, resulting in a semiconductive ternary D-D'-A framework {[Ni-2(bcbp)(2)(H2O)(4)(DMA)](SiW12O40)}(n) (SiW@Ni-bcbp, DMA: dimethylacetamide). The obtained material features an unprecedented porous 8-connected bcu-net structure that accommodates nanoscale [alpha-SiW12O40](4-) counterions, displaying uncommon optoelectronic responses. In contrast to binary Ni-bcbp, the SiW@Ni-bcbp framework exhibits distinctive photochromism and robust X-ray responsiveness, which can be attributed to the synergistic effects of the electron reservoir and multiple photoinduced electron transfer originating from the POMs. As a result, the X-ray detector based on SiW@Ni-bcbp demonstrates a sensitivity of 5741.6 mu C Gy(air)(-1) cm(-2) with a low detection limit of 0.49 mu Gy(air) s(-1). Moreover, the devices demonstrated the capability of producing clearness X-ray images, providing a feasible and stable solution for constructing high-performance direct X-ray detectors.
Keyword ：
direct X-ray detector direct X-ray detector metal-organic framework metal-organic framework multiple electron transfer multiple electron transfer photoelectric conversion photoelectric conversion
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| GB/T 7714 | Wei, Qingsong , Liu, Jingyan , Wu, Liang et al. Multiple Electron Transfer in Semiconductive Ternary D-D'-A Metal-Organic Framework for Enhanced X-Ray Detection and Imaging [J]. | SMALL , 2024 . |
| MLA | Wei, Qingsong et al. "Multiple Electron Transfer in Semiconductive Ternary D-D'-A Metal-Organic Framework for Enhanced X-Ray Detection and Imaging" . | SMALL (2024) . |
| APA | Wei, Qingsong , Liu, Jingyan , Wu, Liang , Chen, Fuhai , Ye, Yuanji , Zhang, Shuquan et al. Multiple Electron Transfer in Semiconductive Ternary D-D'-A Metal-Organic Framework for Enhanced X-Ray Detection and Imaging . | SMALL , 2024 . |
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Correction for 'Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging' by Yu-Hua Chen et al., Chem. Sci., 2024, https://doi.org/10.1039/d4sc00735b.
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| GB/T 7714 | Chen, Yu-Hua , Zhang, Guo-Zhen , Chen, Fu-Hai et al. Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging (20 Apr, 10.1039/d4sc00735b, 2024) [J]. | CHEMICAL SCIENCE , 2024 , 15 (21) : 8249-8249 . |
| MLA | Chen, Yu-Hua et al. "Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging (20 Apr, 10.1039/d4sc00735b, 2024)" . | CHEMICAL SCIENCE 15 . 21 (2024) : 8249-8249 . |
| APA | Chen, Yu-Hua , Zhang, Guo-Zhen , Chen, Fu-Hai , Zhang, Shu-Quan , Fang, Xin , Chen, Hong-Ming et al. Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging (20 Apr, 10.1039/d4sc00735b, 2024) . | CHEMICAL SCIENCE , 2024 , 15 (21) , 8249-8249 . |
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The development of high-quality organic scintillators encounters challenges primarily associated with the weak X-ray absorption ability resulting from the presence of low atomic number elements. An effective strategy involves the incorporation of halogen-containing molecules into the system through co-crystal engineering. Herein, we synthesized a highly fluorescent dye, 2,5-di(4-pyridyl)thiazolo[5,4-d]thiazole (Py2TTz), with a fluorescence quantum yield of 12.09%. Subsequently, Py2TTz was co-crystallized with 1,4-diiodotetrafluorobenzene (I2F4B) and 1,3,5-trifluoro-2,4,6-triiodobenzene (I3F3B) obtaining Py2TTz-I2F4 and Py2TTz-I3F3. Among them, Py2TTz-I2F4 exhibited exceptional scintillation properties, including an ultrafast decay time (1.426 ns), a significant radiation luminescence intensity (146% higher than Bi3Ge4O12), and a low detection limit (70.49 nGy s-1), equivalent to 1/78th of the detection limit for medical applications (5.5 mu Gy s-1). This outstanding scintillation performance can be attributed to the formation of halogen-bonding between I2F4B and Py2TTz. Theoretical calculations and single-crystal structures demonstrate the formation of halogen-bond-induced rather than pi-pi-induced charge-transfer cocrystals, which not only enhances the X-ray absorption ability and material conductivity under X-ray exposure, but also constrains molecular vibration and rotation, and thereby reducing non-radiative transition rate and sharply increasing its fluorescence quantum yields. Based on this, the flexible X-ray film prepared based on Py2TTz-I2F4 achieved an ultrahigh spatial resolution of 26.8 lp per mm, underscoring the superiority of this strategy in developing high-performance organic scintillators. Two organic halogen co-crystal scintillators with strong halogen-bond-induced charge-transfer interactions enable a fast response, low detection limit and ultra-high-resolution imaging.
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| GB/T 7714 | Chen, Yu-Hua , Zhang, Guo-Zhen , Chen, Fu-Hai et al. Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging [J]. | CHEMICAL SCIENCE , 2024 , 15 (20) : 7659-7666 . |
| MLA | Chen, Yu-Hua et al. "Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging" . | CHEMICAL SCIENCE 15 . 20 (2024) : 7659-7666 . |
| APA | Chen, Yu-Hua , Zhang, Guo-Zhen , Chen, Fu-Hai , Zhang, Shu-Quan , Fang, Xin , Chen, Hong-Ming et al. Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging . | CHEMICAL SCIENCE , 2024 , 15 (20) , 7659-7666 . |
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通过水热合成法制备了一种基于紫精衍生物的有机-无机超分子光致变色材料，观察了其可逆的光致变色现象，并通过粉末衍射、红外光谱、固体紫外漫反射光谱与电子顺磁共振光谱深入研究了其光致变色机理。
Keyword ：
光致变色 光致变色 有机-无机超分子材料 有机-无机超分子材料 水热合成 水热合成 紫精衍生物 紫精衍生物
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| GB/T 7714 | 张书泉 , 陈颖 , 程云龙 et al. 一种具有光致变色性能的有机-无机超分子材料的合成与性能研究 [J]. | 安徽化工 , 2024 , 50 (01) : 30-33 . |
| MLA | 张书泉 et al. "一种具有光致变色性能的有机-无机超分子材料的合成与性能研究" . | 安徽化工 50 . 01 (2024) : 30-33 . |
| APA | 张书泉 , 陈颖 , 程云龙 , 曹若雨 . 一种具有光致变色性能的有机-无机超分子材料的合成与性能研究 . | 安徽化工 , 2024 , 50 (01) , 30-33 . |
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As an emerging class of hybrid materials, donor-acceptor (D-A) hybrid crystals with photoactive organic and inorganic components have gradually become an ideal platform for photochromic materials. Wherein the most available organic components are electron-poor naphthalenediimide, pyridinium, and triazine derivatives, inorganic units are electron-rich polyoxometalates and metal halides. Herein, we introduced pyridinium moieties into the naphthalenediimide core by conjugated bonds so as to increase the electron deficiency of organic species for enhanced photochromic properties. Four anion-pi interaction directed hybrid crystals, (Me2DPNDI)(3)(PW12O40)(2) (1), (Et2DPNDI)(3)(DMSO)(2)(PMo12O40)(2) (2), (Et2DPNDI)(3)(PW12O40)(2) (3), and (Et2DPNDI)(2)(SiMo12O40) (4), have been obtained, which possess reversible, naked-eye perceptible color changes with varying light response rates. These rates are as follows: 3 > 1 > 4 > 2. As expected, such D-A hybrid crystals with conjugated naphthalenediimide-pyridinium salts feature both photo- and thermally induced electron transfer pathways, along with enhanced anion-pi interactions. Consequently, they demonstrate a higher rate of photochromism compared to those of hybrids containing naphthalenediimide or pyridinium derivatives as organic acceptors.
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| GB/T 7714 | Chen, Jia-Bao , Di, Yi-Ming , Ye, Yuan-Ji et al. Conjugated Naphthalenediimide-Pyridinium Salts in Donor-Acceptor Hybrid Materials for Enhanced Photochromic Properties [J]. | INORGANIC CHEMISTRY , 2024 , 64 (1) : 606-616 . |
| MLA | Chen, Jia-Bao et al. "Conjugated Naphthalenediimide-Pyridinium Salts in Donor-Acceptor Hybrid Materials for Enhanced Photochromic Properties" . | INORGANIC CHEMISTRY 64 . 1 (2024) : 606-616 . |
| APA | Chen, Jia-Bao , Di, Yi-Ming , Ye, Yuan-Ji , Song, Yu-Ping , Zhou, Jia-Hao , You, Ming-Hua et al. Conjugated Naphthalenediimide-Pyridinium Salts in Donor-Acceptor Hybrid Materials for Enhanced Photochromic Properties . | INORGANIC CHEMISTRY , 2024 , 64 (1) , 606-616 . |
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The development of novel building blocks with sp(3)-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors (NFAs), but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs. Herein, two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings (BTPS) or selenophene rings (BTPSe) are designed and synthesized as the donor cores for constructing NFAs (MQX-2 and MQX-4). It is found that replacing the sulfur atoms (MQX-2) at the outer positions of the heteroarene core with selenium atoms (MQX-4) can effectively modulate the molecular packing mode of the NFAs. The incorporation of selenium atoms induces stronger O...Se noncovalent interaction than O...S, thus promoting the formation of mixed H/J-type aggregates in MQX-4. Benefiting from more electron hopping channels, MQX-4 exhibits higher electron transport (more than 1-fold enhancement) and photovoltaic properties compared to MQX-2, which forms only H-type aggregates.
Keyword ：
Electron acceptors Electron acceptors Electron transport Electron transport Molecular packing Molecular packing Noncovalent interactions Noncovalent interactions Polymer solar cells Polymer solar cells
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| GB/T 7714 | Tao, Hongxin , Tang, Changquan , Ma, Yunlong et al. Enhancing Photovoltaic Performance of Ladder-Type Heteroarene-Based Electron Acceptors by Modulating Molecular Packing [J]. | CHINESE JOURNAL OF CHEMISTRY , 2023 , 41 (17) : 2143-2150 . |
| MLA | Tao, Hongxin et al. "Enhancing Photovoltaic Performance of Ladder-Type Heteroarene-Based Electron Acceptors by Modulating Molecular Packing" . | CHINESE JOURNAL OF CHEMISTRY 41 . 17 (2023) : 2143-2150 . |
| APA | Tao, Hongxin , Tang, Changquan , Ma, Yunlong , Zhang, Shu-Quan , Liao, Ruochuan , Tu, Qisheng et al. Enhancing Photovoltaic Performance of Ladder-Type Heteroarene-Based Electron Acceptors by Modulating Molecular Packing . | CHINESE JOURNAL OF CHEMISTRY , 2023 , 41 (17) , 2143-2150 . |
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Controlling the aggregation of small-molecule acceptors (SMAs) is essential to obtain an optimal morphology and to improve the photovoltaic performance of polymer solar cells (PSCs). However, reducing intermolecular aggregation of SMAs is usually accompanied by the disruption of compact molecular packing thereby leading to their decreased electron mobilities. Here, two novel M-series SMAs (MD1T and MD2T) based on ladder-type heterononacenes with neighboring side-chains separated by one or two thiophene rings are designed and synthesized. It is found that shortening the spacing of the neighboring side-chains of the SMAs can greatly alleviate the intermolecular aggregation and alter the molecular orientation from bimodal edge-on/face-on to predominant face-on while maintaining the compact molecular packing. As a result, a more favorable morphology with smaller domain sizes is formed for the MD1T-based blend films, which greatly improves the charge generation and charge transport for the corresponding PSCs. The best-performing MD1T-based device affords an efficiency of 12.43%, over seven times higher than that of the MD2T-based device. This work reveals the importance of the spacing between the neighboring side-chains in modulating the molecular aggregation and active layer morphology, and the obtained structure-performance relationships shall provide important guidance for designing highly efficient SMAs.
Keyword ：
aggregation aggregation molecular orientation molecular orientation neighboring side-chains neighboring side-chains polymer solar cells polymer solar cells small-molecule acceptors small-molecule acceptors
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| GB/T 7714 | Ma, Yunlong , Luan, Shaoxin , Cai, Dongdong et al. Revealing the spacing effect of neighboring side-chains in modulating molecular aggregation and orientation of M-series acceptors [J]. | AGGREGATE , 2023 , 4 (4) . |
| MLA | Ma, Yunlong et al. "Revealing the spacing effect of neighboring side-chains in modulating molecular aggregation and orientation of M-series acceptors" . | AGGREGATE 4 . 4 (2023) . |
| APA | Ma, Yunlong , Luan, Shaoxin , Cai, Dongdong , Zhang, Shu-Quan , Wang, Jin-Yun , Tu, Qisheng et al. Revealing the spacing effect of neighboring side-chains in modulating molecular aggregation and orientation of M-series acceptors . | AGGREGATE , 2023 , 4 (4) . |
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