Crystal Structure and Theoretical Energy Gap of 2-(2-((4- (Pyridin-2-yl)pyrimidin-2-yl)disulfanyl)pyrimidin-4-yl)pyridinium Hexafluorophosphate

摘要
图/表
参考文献
相关文章 (15)

全文: PDF (574 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要

The crystal structure of 2-(2-((4-(pyridin-2-yl)pyrimidin-2-yl)disulfanyl)pyrimidin- 4-yl)pyridinium hexafluorophosphate was obtained by X-ray single-crystal diffraction. This molecule crystallizes in monoclinic P2/c space group with a = 6.219(1), b = 13.103(2), c = 13.059(2) Å, β = 97.567(2)°, Z = 2, the final R = 0.0525 and wR = 0.1434. The title compound was prepared successfully from 1,2-bis(4-(pyridin-3-yl)pyrimidin-2-yl)disulfane (BPPD). TD-DFT computational studies on energy gaps and UV-Vis spectra of BPPD and the title compound have been carried out for comparisons. The resultant HOMO-LUMO gap of the BPPD compound is 4.45 eV, while that for the corresponding hexafluorophosphate salt is much smaller at 2.46 eV, which are in agreement with their UV-Vis absorptions.

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	陶涛
	赵煚珖
	曹晖

关键词 ： pyridinium, hexafluorophosphate, crystal structure, HOMO-LUMO gap

Abstract：

X-射线单晶衍射测定联硫二嘧啶吡啶鎓六氟磷酸盐的晶体结构。该分子结晶在单斜P2/c 空间群，其中a = 6.219(1)，b = 13.103(2)，c = 13.059(2) Å，β = 97.567(2)°，Z = 2，精修之后R = 0.0525，wR = 0.1434。该化合物由原料1,2-双(4-(3-吡啶基)2-嘧啶基)二硫化合物(BPPD)成功制得。为了深入对比成盐前后二者性能的差异，利用含时密度泛函计算其能隙和紫外-可见光谱。化合物BPPD的HOMO-LUMO能隙为4.45 eV，而鎓盐的能隙更小，为2.46 eV，该计算结果与其紫外-可见光谱的数据一致。

Key words： pyridinium hexafluorophosphate crystal structure HOMO-LUMO gap

收稿日期: 2016-04-28 出版日期: 2017-02-13

基金资助:

This project was supported by the National Natural Science Foundation of China (No. 21501097), the Natural Science Foundation of Jiangsu Province (No. BK20150890), the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No. 15KJB150021),and the Startup Foundation for Introducing Talent of NUIST

通讯作者: taotao@nuist.edu.cn E-mail: taotao@nuist.edu.cn

引用本文:

陶涛;赵煚珖;曹晖. Crystal Structure and Theoretical Energy Gap of 2-(2-((4- (Pyridin-2-yl)pyrimidin-2-yl)disulfanyl)pyrimidin-4-yl)pyridinium Hexafluorophosphate[J]. 结构化学, 2017, 36(2): 229-235.
TAO Tao;ZHAO Jiong-Guang;CAO Hui . 联硫二嘧啶吡啶鎓六氟磷酸盐的晶体结构与理论能隙. CHINESE JOURNAL OF STRUCTURNAL CHEMISTRY, 2017, 36(2): 229-235.

链接本文:

http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2017/V36/I2/229

REFERENCES
(1)Varela, L. M.; Mendez-Morales, T.; Carrete, J.; Gomez-Gonzalez, V.; Docampo-Alvarez, B.; Gallego, L. J.; Cabeza, O.; Russina, O. Solvation of molecular cosolvents and inorganic salts in ionic liquids: A review of molecular dynamics simulations. J. Mol. Liq. 2015, 210, 178188.
(2) Frere, P.; Skabara, P. J. Salts of extended tetrathiafulvalene analogues: relationships between molecular structure, electrochemical properties and solid state organisation. Chem. Soc. Rev. 2005, 34, 6998.
(3) Zhang, J. L.; Jiang, M.; Xing, L. B.; Qin, K.; Liu, T. Z.; Zhou, J.; Si, W. J.; Cui, H. Y.; Zhuo, S. P. Three dimensional sulfur-doped graphene hydrogels with tetrathiafulvalene for high performance supercapacitors. Chin..J. Chem. 2016, 34, 4652.
(4) Chen, B.; Lv, Z. P.; Hua, C.; Leong, C. F.; Tuna, F.; D’Alessandro, D. M.; Collison, D.; Zuo, J. L. Dinuclear ruthenium complex based on a π-extended bridging ligand with redox-active tetrathiafulvalene and 1,10-phenanthroline units. Inorg. Chem. 2016, 55, 46064615.
(5) Zhu, H. B.; Wu, Y. F.; Zhao, Y.; Hu J. Unprecedented metal-mediated in situ reactions of heterocyclic disulfide of di[4-(pyridin-2-yl)pyrimidinyl]disulfide. Dalton Trans. 2014, 43, 1715617162.
(6) Tao, T.; Peng, Y. X.; Huang, W.; You, X. Z. Coplanar bithiazole-centered heterocyclic aromatic fluorescent compounds having different donor/acceptor terminal groups. J. Org. Chem. 2013, 78, 24722481.
(7) Tao, T.; Ma, B. B.; Peng, Y. X.; Wang, X. X.; Huang, W.; You, X. Z. Asymmetrical/symmetrical D−π–A/D−π–D thiazole-containing aromatic heterocyclic fluorescent compounds having the same triphenylamino chromophores. J. Org. Chem. 2013, 78, 86698679.
(8) Ji, J. F.; Li, L.; Zhu, H. B. 4,4. '-Di-3-pyridyl-2,2. '-dithiodipyrimidine. Acta Crystallogr., Sect. E 2009, 65, 1253.
(9) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Solution. University of Göttingen, Germany 1997.
(10) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Pittsburgh PA 2009, Gaussian 09, Revision C.01.
(11) Roncali, J. Molecular engineering of the band gap of π-conjugated systems: Facing technological applications. Macromol. Rapid Commun. 2007, 28, 17611775.
(12) Pilia, L.; Pizzotti, M.; Tessore, F.; Robertson, N. Tuning the LUMO energy of 1,10-phenanthroline in alpha-diimine-dithiolate Ni(II) complex and enhancement of nonlinear optical properties. Inorg. Chim. Acta 2015, 430, 114119.
(13) Albero, J.; Asiri, A. M.; Garcia, H. Influence of the composition of hybrid perovskites on their performance in solar cells. J. Mater. Chem. A 2016, 4, 43534364.