Citation: Wen-Xu ZHENG, Tao LI, Zheng XIANG, Chang-Cang HUANG. Cytosinium Isophthalate: Crystal Structure Redetermination and Room Temperature Phosphorescence[J]. Chinese Journal of Structural Chemistry, ;2020, 39(9): 1707-1713. doi: 10.14102/j.cnki.0254-5861.2011-2647 shu

Cytosinium Isophthalate: Crystal Structure Redetermination and Room Temperature Phosphorescence

College of Chemistry, Fuzhou University, Fuzhou 350108, China

Corresponding author: Chang-Cang HUANG, cchuang@fzu.edu.cn
Received Date: 24 October 2019
Accepted Date: 19 January 2020

Fund Project: the Natural Science Foundation of Fujian Province 2018J01688

Figures(8)

The title compound cytosinium isophthalate (C-H₂IA) self-assembly of cytosine (C) and isophthalic acid (H₂IA) in aqueous media has been synthesized and the crystal structure with a reasonable protonation state is redetermined. Single-crystal X-ray diffraction analysis reveals that each asymmetric unit contains one protoned cytosine molecule and one deprotoned isophthalic acid. The proton transferred from carboxylic acid to the pyrimidine ring is disordered across an inversion center with occupancy of 0.5 and the proton located to one of the carboxylate group lies on an inversion center shared by two crystallographically equivalent oxygen atoms. In addition, the cytosine molecules are connected by complementary hydrogen bonds to form a one-dimensional tape structure. The neighboring isophthalic acids are connected via hydrogen bonds between carboxyl groups to form a one-dimensional lattice like tape. Furthermore, the adjacent organic base tapes and organic acid tapes are stacked one with another through π-π stacking interactions to form a three-dimensional supramolecular structure. Interestingly, C-H₂IA displays a green phosphorescence in solid state at room temperature with the lifetime of 0.7 s determined by time resolved studies, indicating that supramolecular C-H₂IA is a potential pure organic phosphorescent luminogens.
- cytosinium isophthalate,
- crystal structure redetermination,
- room temperature phosphorescence,
- supramolecular framework
1. [1]
  Yang, Z.; Mao, Z.; Zhang, X. Intermolecular electronic coupling of organic units for efficient persistent room-temperature phosphorescence. Angew. Chem., Int. Ed. Engl. 2016, 55, 2181–2185. doi: 10.1002/anie.201509224
2. [2]
  (a) Kuei, C. Y.; Liu, S. H.; Chou, P. T. Room temperature blue phosphorescence: a combined experimental and theoretical study on the bis-tridentate Ir(Ⅲ) metal complexes. Dalton Trans. 2016, 45, 15364–15373; (b) Hirata, S. Recent advances in materials with room-temperature phosphorescence: photophysics for triplet exciton stabilization. Adv. Optical Mater. 2017, 5, 1700116–1700165.
3. [3]
  (a) Gong, Y.; Chen, G.; Peng, Q. Achieving persistent room temperature phosphorescence and remarkable mechanochromism from pure organic luminogens. Adv. Mater. 2015, 27, 6195–6201; (b) Xiao, L.; Wu, Y.; Chen, J. Highly efficient room-temperature phosphorescence from halogen-bonding-assisted doped organic crystals. J. Phys. Chem. A 2017, 121, 8652–8658.
4. [4]
  (a) Ge, C. H.; Zhang, X. Y.; Yu, F. Hydrogen-bonded assembly of Ni(Ⅱ) and Cu(Ⅱ) complexes generate 3D supramolecular frameworks. J. Chem. Crystallogr. 2008, 38, 501–505; (b) Nirmalram, J. S.; Tamilselvi, D.; Muthiah, P. T. Hydrogen bonded supramolecular assembly in N₆-benzyladeninium nitrate and N₆-benzyladeninium 3-hydroxy picolinate: a synthetic cytokinin. J. Chem. Crystallogr. 2011, 41, 864–867.
5. [5]
  Chen, J. The complexation between 'texas sized' molecular box and linear n-aliphate dianion: en route to supramolecular organic frameworks (SOFs) for selectively CO₂ absorption. Tetrahedron 2016, 72, 431–435. doi: 10.1016/j.tet.2015.11.062
6. [6]
  Ni, X. L.; Chen, S.; Yang, Y. Facile cucurbit[8]uril-based supramolecular approach to fabricate tunable luminescent materials in aqueous solution. J. Am. Chem. Soc. 2016, 138, 6177–6183. doi: 10.1021/jacs.6b01223
7. [7]
  Han, Z. B.; Xiao, Z. Z.; Hao, M. Functional hydrogen-bonded supramolecular framework for K⁺ ion sensing. Cryst. Growth Des. 2015, 15, 531–533. doi: 10.1021/cg501259g
8. [8]
  Lin, X. M.; Niu, J. L.; Wen, P. X. A polyhedral metal-organic framework based on supramolecular building blocks: catalysis and luminescent sensing of solvent molecules. Cryst. Growth Des. 2016, 16, 4705–4710. doi: 10.1021/acs.cgd.6b00779
9. [9]
  Zhang, Y.; Zhan, T. G.; Zhou, T. Y. Fluorescence enhancement through the formation of a single-layer two-dimensional supramolecular organic framework and its application in highly selective recognition of picric acid. Chem. Comm. 2016, 52, 7588–7591. doi: 10.1039/C6CC03631G
10. [10]
  Bian, L.; Shi, H.; Wang, X. Simultaneously enhancing efficiency and lifetime of ultralong organic phosphorescence materials by molecular self-assembly. J. Am. Chem. Soc. 2018, 140, 10734–10739. doi: 10.1021/jacs.8b03867
11. [11]
  Ebenezer, S.; Muthiah, P. T. Design of co-crystals/salts of aminopyrimidines and carboxylic acids through recurrently occurring xynthons. Cryst. Growth Des. 2012, 12, 3766–3785. doi: 10.1021/cg3005954
12. [12]
  Ayed, M.; Ayed, B.; Haddad, A. Synthesis and structural characterization of new inorganic-organic hybrid: arsenomolybdate compound with cytosinium cations. Bull. Mater. Sci. 2015, 38, 13–21. doi: 10.1007/s12034-014-0805-8
13. [13]
  Marsh, R. E.; Bierstedt, R.; Eichhorn, E. L. The crystal structure of cytosine-5-acetic acid. Acta Crystallogr. 1962, 15, 310–316. doi: 10.1107/S0365110X62000791
14. [14]
  Perumalla, S. R.; Suresh, E.; Pedireddi, V. R. Nucleobases in molecular recognition: molecular adducts of adenine and cytosine with COOH functional groups. Angew. Chem., Int. Ed. Engl. 2005, 44, 7752–7757. doi: 10.1002/anie.200502434
15. [15]
  Macrae, C. F.; Bruno, I. J.; Chisholm, J. A. Mercury CSD 2.0 - new features for the visualization and investigation of crystal structures. Journal of Applied Crystallogr. 2008, 41, 466–470. doi: 10.1107/S0021889807067908
16. [16]
  (a) Turner, M. J.; McKinnon, M. J. J.; Wolff, S. K.; Grimwood, D. J.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer17 (2017). University of Western Australia. http://hirshfeldsurface.net 2017; (b) Mackenzie, C. F.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer model energies and energy frameworks: extension to metal coordination compounds, organic salts, solvates and open-shell systems. IUCrJ 2017, 4, 575–587; (c) Bakavoli, M.; Rahimizadeh, M.; Feizyzadeh, B. 3,6-di(p-chlorophenyl)-2,7-dihydro-1,4,5-thiadiazepine: crystal structure and decoding intermolecular interactions with hirshfeld surface analysis. J. Chem. Crystallogr. 2010, 40, 746–752.
1. [1]
  Dian-Xue Ma , Yu-Wu Zhong . Achieving highly-efficient room-temperature phosphorescence with a nylon matrix. Chinese Journal of Structural Chemistry, 2024, 43(9): 100391-100391. doi: 10.1016/j.cjsc.2024.100391
2. [2]
  Zeyin Chen , Jiaju Shi , Yusheng Zhou , Peng Zhang , Guodong Liang . Polymer microparticles with ultralong room-temperature phosphorescence for visual and quantitative detection of oxygen through phosphorescence image and lifetime analysis. Chinese Chemical Letters, 2025, 36(5): 110629-. doi: 10.1016/j.cclet.2024.110629
3. [3]
  Xinhui Fan , Yonghao Fan , Yuli Dang , Puhui Xie , Xin Li , Zhanqi Cao , Song Jiang , Lijie Liu , Xin Zheng , Lixia Xie , Caoyuan Niu , Guoxing Liu , Yong Chen . Logically ordered control of organic room-temperature long-lived supramolecular luminophors. Chinese Chemical Letters, 2025, 36(8): 110648-. doi: 10.1016/j.cclet.2024.110648
4. [4]
  Kun Zhang , Ni Dan , Dan-Dan Ren , Ruo-Yu Zhang , Xiaoyan Lu , Ya-Pan Wu , Li-Lei Zhang , Hong-Ru Fu , Dong-Sheng Li . A small D-A molecule with highly heat-resisting room temperature phosphorescence for white emission and anti-counterfeiting. Chinese Journal of Structural Chemistry, 2024, 43(3): 100244-100244. doi: 10.1016/j.cjsc.2024.100244
5. [5]
  Jiayin Zhou , Depeng Liu , Longqiang Li , Min Qi , Guangqiang Yin , Tao Chen . Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting. Chinese Chemical Letters, 2024, 35(11): 109929-. doi: 10.1016/j.cclet.2024.109929
6. [6]
  Jianmei Guo , Yupeng Zhao , Lei Ma , Yongtao Wang . Ultra-long room temperature phosphorescence, intrinsic mechanisms and application based on host-guest doping systems. Chinese Journal of Structural Chemistry, 2024, 43(9): 100335-100335. doi: 10.1016/j.cjsc.2024.100335
7. [7]
  Hong Yao , Feixiang Yang , Jianpeng Hu , Wenyu Cao , Shuning Qin , Tai-Bao Wei , Bingbing Shi , Qi Lin . Ultralong room temperature phosphorescence and broad color-tunability persistent luminescence via new strategy. Chinese Chemical Letters, 2025, 36(6): 110375-. doi: 10.1016/j.cclet.2024.110375
8. [8]
  Bo Yang , Suqiong Yan , Shirong Ban , Wei Huang . New horizons in phosphorus-based emitters: From circularly polarized fluorescence to room-temperature phosphorescence. Chinese Chemical Letters, 2025, 36(11): 110837-. doi: 10.1016/j.cclet.2025.110837
9. [9]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
10. [10]
  Wenya DING , Fangfei XU , Jiayu GU , Xinran CHEN , Kai CHEN . Synthesis and crystal structure of three cucurbit[6]uril-cadmium supramolecular assemblies. Chinese Journal of Inorganic Chemistry, 2026, 42(4): 808-816. doi: 10.11862/CJIC.20260012
11. [11]
  Youbo HU , Donggang LI , Changhua SUN , Zhenzhong LU , Songjun GU . Coordination polymers based on anthracene- and pyrene-derived ligands: Crystal structure, fluorescent property, and framework isomerization. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1681-1688. doi: 10.11862/CJIC.20250004
12. [12]
  Linnan Jiang , Zhenkai Qian , Yong Chen , Xiaoyong Yu , Yugui Qiu , Wen-Wen Xu , Yonghui Sun , Xiufang Xu , Lihua Wang , Yu Liu . Double response reversible phosphorescence based on cyclodextrin supramolecular flexible elastic achieved multicolor delayed fluorescence. Chinese Chemical Letters, 2025, 36(8): 110676-. doi: 10.1016/j.cclet.2024.110676
13. [13]
  Xinyu Zeng , Zhuofan Zeng , Qingqing Hu , Kejun Liu , Lei Ming , Bei Cheng , Wang Wang , Guoqiang Luo , Shaowen Cao . Hierarchical Pt/NiO hollow nanofibers for catalytic oxidation of HCHO at room temperature. Chinese Journal of Structural Chemistry, 2025, 44(6): 100575-100575. doi: 10.1016/j.cjsc.2025.100575
14. [14]
  Ping Liu , Fei Yu . Covalent organic framework ionomers for medium-temperature fuel cells. Chinese Journal of Structural Chemistry, 2025, 44(4): 100465-100465. doi: 10.1016/j.cjsc.2024.100465
15. [15]
  Xianya Yao , Ning Han , Hui Liu , Lingbao Xing . Construction of donor-acceptor supramolecular organic framework with enhanced superoxide anion radical generation for photocatalytic synthesis of benzimidazole. Chinese Chemical Letters, 2026, 37(5): 111426-. doi: 10.1016/j.cclet.2025.111426
16. [16]
  Siwei Wang , Fanxu Zeng , Yuan Yan , Jinghai Liu , Wei-Lei Zhou , Yong Chen . Monochromophore-tunable supramolecular fluorescence-phosphorescence dual light-harvesting NIR emission for multi-dimensional information encryption. Chinese Chemical Letters, 2026, 37(4): 112002-. doi: 10.1016/j.cclet.2025.112002
17. [17]
  Yu Hong , Yuqian Jiang , Chenhuan Yuan , Decai Wang , Yimeng Sun , Jian Jiang . Unraveling temperature-dependent supramolecular polymorphism of naphthalimide-substituted benzene-1,3,5-tricarboxamide derivatives. Chinese Chemical Letters, 2024, 35(12): 109909-. doi: 10.1016/j.cclet.2024.109909
18. [18]
  Xiaoqian Wang , Yanling Shen , Long Chen , Lizhi Fang , Kuppusamy Kanagaraj , Ming Rao , Chunying Fan , Wanhua Wu , Cheng Yang . Azobenzene-winged phenanthroline for supramolecular chirality sensing and multidimensional chiroptical manipulation via solvent, light, temperature, and redox. Chinese Chemical Letters, 2026, 37(2): 111710-. doi: 10.1016/j.cclet.2025.111710
19. [19]
  Shuai Zhu , Mingjie Chen , Haichao Shen , Hanming Ding , Wenbo Li , Junliang Zhang . Palladium/Xu-Phos-catalyzed enantioselective arylalkoxylation reaction of γ-hydroxyalkenes at room temperature. Chinese Chemical Letters, 2024, 35(11): 109879-. doi: 10.1016/j.cclet.2024.109879
20. [20]
  Zi-Yi Yu , Gen-Feng Li , Zhe-Kun Xu , Lipeng Long , Yan Qin , Zi-Yi Du , Zhong-Xia Wang . Enantiomeric organic amine-borane adduct crystals with room-temperature multi-channel switches. Chinese Journal of Structural Chemistry, 2025, 44(11): 100715-100715. doi: 10.1016/j.cjsc.2025.100715

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(1638)
HTML views(52)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142