Citation: Yu-Kong LI, Yu-Hui TAN, Yao LIU, Yun-Zhi TANG, Wen-Juan WEI, Ning SONG, Peng-Kang DU, Ding-Chong HAN. Syntheses, Crystal Structures, SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(Ⅱ) and Substituted Benzyl Triphenylphosphonium Cations[J]. Chinese Journal of Structural Chemistry, ;2021, 40(6): 739-745. doi: 10.14102/j.cnki.0254–5861.2011–3012 shu

Syntheses, Crystal Structures, SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(Ⅱ) and Substituted Benzyl Triphenylphosphonium Cations

Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China

Corresponding author: Yu-Hui TAN, tyxcn@163.com
Received Date: 27 October 2020
Accepted Date: 4 December 2020

Fund Project: the National Natural Science Foundation of China 21761013the National Natural Science Foundation of China 21671086the National Natural Science Foundation of China 21471070

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Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)⁺·[Mn(NCS)₄]^2- (1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn²⁺ ions are tetra-coordinated with N atoms of four NCS^- ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)₄^2- forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation (SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate (KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.
- benzyltriphenylphonium chloride,
- crystal structure,
- SHG responses,
- luminescent properties
1. [1]
  Liu, C.; Mei, D. J.; Cao, W. Z.; Yang, Y.; Wu, Y. D.; Li, G. B.; Lin, Z. S. Mn-Based tin sulfide Sr₃MnSn₂S₈ with a wide band gap and strong nonlinear optical response. J. Mater. Chem. 2019, 7, 1146–1150.
2. [2]
  Tang, Y. Z.; Yu, Y. M.; Xiong, J. B.; Tan, Y. H.; Wen, H. R. Unusual high-temperature reversible phase-transition behavior, structures, and dielectric-ferroelectric properties of two new crown ether clathrates. J. Am. Chem. Soc. 2015, 137, 13345–13351. doi: 10.1021/jacs.5b08061
3. [3]
  Chen, S. P.; Wang, C. F.; Zhou, H. T.; Tan, Y. H.; Wen, H. R.; Tang, Y. Z. Ferroelectric property, switchable dielectric, and excellent second harmonic generation response in a homochiral organic salt: l-prolinammonium 1-adamantane carboxylate. Cryst. Growth Des. 2018, 18, 6117–6122. doi: 10.1021/acs.cgd.8b00994
4. [4]
  Antorrena, G. .; Palacio, F.; Castro, M.; Pellaux, R.; Decurtins, S. Thermal and magnetic study of mixed-metal oxalate-bridged 2D magnets. J. Magn. Magn. Mater. 1999, 196, 581–583.
5. [5]
  Hollingsworth, M. D. Crystal engineering: from structure to function. Science 2002, 295, 2410–2413. doi: 10.1126/science.1070967
6. [6]
  Galet, A.; Muñoz, M. C.; Gaspar, A. B.; Real, J. A. Architectural isomerism in the three-dimensional polymeric spin crossover system {Fe(pmd)₂[Ag(CN)₂]₂}: synthesis, structure, magnetic properties, and calorimetric studies. Inorg. Chem. 2005, 24, 8749–8755.
7. [7]
  Wernsdorfer, W.; Aliaga-Alcalde, N.; Hendrickson, D. N.; Christou, G. Exchange-biased quantum tunneling in a supramolecular dimer of single-molecule magnets. Nature 2002, 416, 406–409. doi: 10.1038/416406a
8. [8]
  Yang, E. C.; Zhao, H. K.; Ding, B.; Wang, X. G.; Zhao, X. J. Four novel three-dimensional triazole-based zinc(Ⅱ) metal-organic frameworks controlled by the spacers of dicarboxylate ligands: hydrothermal synthesis, crystal structure, and luminescence properties. Cryst. Growth Des. 2007, 7, 2009–2015. doi: 10.1021/cg070356n
9. [9]
  Hu, R. F.; Zhang, J.; Kang, Y.; Yao, Y. G. A fluorescent Zn-benzotriazole 2D polymer with (6, 3) topology. Inorg. Chem. Commun. 2005, 8, 828–830. doi: 10.1016/j.inoche.2005.06.017
10. [10]
  Chen, J. L.; Guo, Z. H.; Luo, Y. S.; Qiu, L.; He, L. H.; Liu, S. J.; Wen, H. R.; Wang, J. Y. Luminescent monometallic Cu(I) triphenylphosphine complexes based on methylated 5-trifluoromethyl-3-(2΄-pyridyl)-1, 2, 4-triazole ligands. New J. Chem. 2016, 40, 5325–5332. doi: 10.1039/C5NJ03529E
11. [11]
  Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339−341. doi: 10.1107/S0021889808042726
12. [12]
  Sheldrick, G. M. SHELXS-97, Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997.
13. [13]
  Yu, Y. Z.; Chang, S. Y.; Han, X.; Chen, G. X.; Xuan, Y. W.; Wu, X. L.; Wang, F. Hydrothermal synthesis, crystal structure and luminescence property of a 2D manganese(Ⅱ) coordination polymer. Chin. J. Struct. Chem. 2019, 38, 147–154.
14. [14]
  Chen, X.; Dai, S. L.; Cheng, Z. P.; Liang, L. B.; Han, S.; Liu, J. F.; Zhou, J. R.; Yang, L. M.; Ni, C. L. Syntheses, crystal structures, and magnetic properties of two hybrid materials self-assembly from tetra(isothiocyanate)cobalt(Ⅱ) anion and substituted benzyl triphenylphosphinium. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nan-Metal Chemistry 2012, 42, 987–993. doi: 10.1080/15533174.2012.680114
15. [15]
  Chen, H. J.; Zhang, L. Z.; Cai, Z. G.; Yang, G.; Chen, X. M. Organic-inorganic hybrid materials assembled through weak intermolecular interactions. synthesis, structures and non-linear optical properties of [4, 4΄-bipyH₂][M(NCS)₄] (M = Mn²⁺, Co²⁺ or Zn²⁺; 4, 4΄-bipy = 4, 4΄-bipyridine). J. Chem. Soc. Dalton Trans. 2000, 14, 2463–2466.
16. [16]
  Bleiholder, C.; Werz, D. B.; Koppel, H.; Gleiter, R. Theoretical investigations on chalcogen-chalcogen interactions: what makes these nonbonded interactions bonding? J. Am. Chem. Soc. 2006, 128, 2666–2674. doi: 10.1021/ja056827g
17. [17]
  Liu, X. M.; Lu, X. Z.; Fu. F.; Liu, B.; Hu, H. M.; Gao, Q. C.; Wang, J. W.; Xue, G. L. Synthesis and crystal structure of a novel charge transfer salt, (TMT-TTF)₄[HPMo₁₂O₄₀]. J. Mol. Struct. 2005, 751, 17–21. doi: 10.1016/j.molstruc.2005.05.003
18. [18]
  Bleiholder, C.; Gleiter, R.; Werz. D. B.; Köppel, H. Theoretical investigations on heteronuclear chalcogen-chalcogen interactions: on the nature of weak bonds between chalcogen lefts. Inorg. Chem. 2007, 46, 2249–2260. doi: 10.1021/ic062110y
19. [19]
  Steiner, T. The hydrogen bond in the solid state. Angew. Chem. Int. Ed. 2002, 41, 48–76. doi: 10.1002/1521-3773(20020104)41:1<48::AID-ANIE48>3.0.CO;2-U
20. [20]
  Chen, X.; Chen, W. Q.; Han, S.; Liu, J. F.; Zhou, J. R.; Yu, L. L.; Yang, L. M.; Ni, C. L.; Hu, X. L. Two hybrid materials self-assembly from tetra(isothiocyanate)cobalt(Ⅱ) dianion and substituted benzyl triphenylphosphinium. J. Mol. Struct. 2010, 984, 164–169. doi: 10.1016/j.molstruc.2010.09.022
21. [21]
  Ye, H. Q.; Xie, J. L.; Yu, J. Y.; Liu, Q. T.; Dai, S. L.; Huang, W. Q.; Zhou, J. R.; Yang, L. M.; Ni, C. L. Syntheses, crystal structures, luminescent properties of two new molecular solids with tetra(isothiocyanate)zinc(Ⅱ) and substituted benzyl triphenylphosphonium cations. Synthetic Metals. 2014, 197, 99–104. doi: 10.1016/j.synthmet.2014.09.006
22. [22]
  Yang, H. L.; Chen, F.; He, X.; Li, Y.; Zhang, X. Q. Synthesis, crystal structure, thermal stability, luminescence and magnetic property of a new Mn(Ⅱ) coordination polymer. Chin. J. Struct. Chem. 2018, 37, 1834–1841.
23. [23]
  Zhou, H. T.; Yang, K.; Liu, Y.; Tang, Y. Z.; Wei, W. J.; Shu, Q.; Zhao, J. J.; Tan, Y. H. In situ [2 + 3] cycloaddition synthesis, crystal structures, strong SHG responses and fluorescence properties of three novel Zn coordination polymers. Chin. Chem. Lett. 2019, 31, 841–845.
24. [24]
  Fan, X. W.; Liu, Y.; Tang, Y. Z.; Wei, W. J.; Zhang, J. C.; Luo, Z. Y.; Wang, C. F.; Tan, Y. H. High-temperature reversible phase-transition behavior, switchable dielectric and second harmonic generation response of two homochiral crown ether clathrates. Chem. Asian J. 2019, 14, 2203–2209. doi: 10.1002/asia.201900512
25. [25]
  Tang, Y. Z.; Zhou, M.; Huang, J.; Tan, Y. H.; Wu, J. S.; Wen, H. R. In situ synthesis and ferroelectric, SHG response, and luminescent properties of a novel 3D acentric zinc coordination polymer. Inorg. Chem. 2013, 52, 1679–1681. doi: 10.1021/ic302411r
26. [26]
  Gao, J. X.; Xiong, J. B.; Xu, Q.; Tan, Y. H.; Liu, Y.; Wen, H. R.; Tang, Y. Z. Supramolecular interactions induced chirality transmission, second harmonic generation responses, and photoluminescent property of a pair of enantiomers from in situ [2 + 3] cycloaddition synthesis. Cryst. Growth Des. 2016, 16, 1559–1564. doi: 10.1021/acs.cgd.5b01684
27. [27]
  Liu, Y.; Zhou, H. T.; Chen, S. P.; Tan, Y. H.; Wang, C. F.; Yang, C. S.; Wen, H. R.; Tang, Y. Z. reversible phase transition and switchable dielectric behaviors triggered by rotation and order-disorder motions of crowns. Dalton Trans. 2018, 47, 3851–3856. doi: 10.1039/C8DT00003D
28. [28]
  Yang, K.; Yang, C. S.; Dong, X. X.; Tan, Y. H.; Tang, Y. H.; Wei, W. J. Two rare-earth molecular ferroelectrics with high curie temperatures, large spontaneous polarization, switchable second harmonic generation effects, and strong photoluminescence. Chemistry-A European Journal 2020, 26, 5887–5892. doi: 10.1002/chem.202000188
29. [29]
  Yang, K.; Dong, X. X.; Xu, Q.; Tan, Y. H.; Tang, Y. Z. Nopinic acid is an unprecedented homochiral single-component organic ferroelectric. Appl. Mater. Today 2020, 20, 100687. doi: 10.1016/j.apmt.2020.100687
30. [30]
  Fan, H. L.; Lin, C. S.; Chen, K. C.; Peng, G.; Li, B. X.; Zhang, G.; Long, X. F.; Ye, N. (NH₄)Bi₂(IO₃)₂F₅: an unusual ammonium-containing metal iodate fluoride showing strong second harmonic generation response and thermochromic behavior. Angew. Chem. Int. Ed. 2020, 59, 5268–5272. doi: 10.1002/anie.201913287
31. [31]
  Li, F. F.; Lu, L. P. A new Mn(Ⅱ) coordination polymer: synthesis, structure and magnetic property. Chin. J. Struct. Chem. 2019, 38, 1814–1822.
32. [32]
  Shi, C.; Ma, J. J.; Jiang, J. Y.; Hua, M. M.; Xu, Q.; Yu, H.; Zhang, Y.; Ye, H. Y. Large piezoelectric response in hybrid rare-earth double perovskite relaxor ferroelectric. J. Am. Chem. Soc. 2020, 142, 9634–9641.
33. [33]
  Savard, D.; Leznoff, D. B. Synthesis, structure and light scattering properties of tetraalkylammonium metal isothiocyanate salts. Dalton Trans. 2013, 42, 14982–14991. doi: 10.1039/c3dt50974e
34. [34]
  Li, Q.; Shi, P. P.; Ye, Q.; Wang, H. T.; Wu, D. H.; Ye, H. Y.; Fu, D. W.; Zhang, Y. A switchable molecular dielectric with two sequential reversible phase transitions: [(CH₃)₄P]₄[Mn(SCN)₆]. Inorg. Chem. 2015, 54, 10642−10647. doi: 10.1021/acs.inorgchem.5b01437
35. [35]
  Neumann, T.; Jess, I.; Näther, C. Crystal structures of bis[4-(dimethylamino)-pyridinium] tetrakis(thiocyanato-κN) manganate(Ⅱ) and tris[4-(dimethylamino)pyridinium] pentakis-(thiocyanato-κN)manganate(Ⅱ). Acta Cryst. 2018, E74, 15–20.
36. [36]
  Wang, C. F.; Fan, X. W.; Tan, Y. H.; Wei, W. J.; Tang, Y. Z. High-temperature reversible phase transition and switchable dielectric and semiconductor properties in a 2D hybrid [(C₃H₁₂N₂O)CdCl₄]_n. Eur. J. Inorg. Chem. 2019, 2907–2911.
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