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A green approach to the preparation of triangular silver(I) 3,5-bis(trifluoromethyl)pyrazolate: crystal structures of two adducts with triethylammonium nitrate or benzoic acid

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Abstract

An improved procedure is described herein for the synthesis of triangular Ag(I) 3,5-bis(trifluoromethyl)pyrazolate ({[3,5-(CF3)2Pz]Ag}3), which involves initial preparation of its adducts with triethylammonium nitrate or benzoic acid, namely {[3,5-(CF3)2Pz]Ag}3·(Et3NH·NO3)2 (1) and {[3,5-(CF3)2Pz]Ag}3·(PhCOOH)2 (2), followed by removal of the nitrate and benzoic acid by washing or extraction with water to afford the pristine trisilver complex {[3,5-(CF3)2Pz]Ag}3. X-ray diffraction analysis on 1 and 2 reveals that {[3,5-(CF3)2Pz]Ag}3, acting as a π-acidic host, can combine with guest molecules/ions (NO3−, PhCOOH) by weak Ag–O/C coordination bonds, π–π stacking and C–H···F interactions. Our proposed synthetic procedure for {[3,5-(CF3)2Pz]Ag}3 can be easily carried out at room temperature, without using complex Schlenk techniques or hazardous organic solvents such as benzene and toluene, thus representing a green and facile approach to this well-recognized π-acidic complex.

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References

  1. Mezei G, Zaleski CM, Pecoraro VL (2007) Structural and functional evolution of metallacrowns. Chem Rev 107(11):4933–5003

    Article  CAS  Google Scholar 

  2. Yang G, Raptis RG (2003) Supramolecular assembly of trimeric gold(I) pyrazolates through aurophilic attractions. Inorg Chem 42(2):261–263

    Article  CAS  Google Scholar 

  3. Yang G, Baran P, Martínez AR, Raptis RG (2013) Substituent effects on the supramolecular aggregation of AgI-pyrazolato trimers. Cryst Growth Des 13(1):264–269

    Article  CAS  Google Scholar 

  4. Fujisawa K, Ishikawa Y, Miyashita Y, Okamoto K-i (2010) Pyrazolate-bridged group 11 metal(I) complexes: substituent effects on the supramolecular structures and physicochemical properties. Inorg Chim Acta 363(12):2977–2989

    Article  CAS  Google Scholar 

  5. Ni W-X, Li M, Zheng J, Zhan S-Z, Qiu Y-M, Ng SW, Li D (2013) Approaching white-light emission from a phosphorescent trinuclear gold(I) cluster by modulating its aggregation behavior. Angew Chem Int Ed 52(50):13472–13476

    Article  CAS  Google Scholar 

  6. Halcrow MA (2009) Pyrazoles and pyrazolides—flexible synthons in self-assembly. Dalton Trans. https://doi.org/10.1039/B815577A

    Article  Google Scholar 

  7. Mohamed AA (2010) Advances in the coordination chemistry of nitrogen ligand complexes of coinage metals. Coord Chem Rev 254(17):1918–1947

    Article  CAS  Google Scholar 

  8. Pérez J, Riera L (2009) Pyrazole complexes and supramolecular chemistry. Eur J Inorg Chem 33:4913–4925

    Article  Google Scholar 

  9. Duan P-C, Wang Z-Y, Chen J-H, Yang G, Raptis RG (2013) Trigonal prismatic Cu(I) and Ag(I) pyrazolato nanocage hosts: encapsulation of S8 and hydrocarbon guests. Dalton Trans 42(42):14951–14954

    Article  CAS  Google Scholar 

  10. Chen J-H, Liu Y-M, Zhang J-X, Zhu Y-Y, Tang M-S, Ng SW, Yang G (2014) Halogen-involving weak interactions manifested in the crystal structures of silver(I) or gold(I) 4-halogenated-3,5-diphenylpyrazolato trimers. CrystEngComm 16(23):4987–4998

    Article  CAS  Google Scholar 

  11. Titov AA, Filippov OA, Epstein LM, Belkova NV, Shubina ES (2018) Macrocyclic copper(I) and silver(I) pyrazolates: principles of supramolecular assemblies with Lewis bases. Inorg Chim Acta 470:22–35

    Article  CAS  Google Scholar 

  12. Dias HVR, Diyabalanage HVK, Rawashdeh-Omary MA, Franzman MA, Omary MA (2003) Bright phosphorescence of a trinuclear copper(I) complex: luminescence thermochromism, solvatochromism, and “concentration luminochromism”. J Am Chem Soc 125(40):12072–12073

    Article  CAS  Google Scholar 

  13. Rasika Dias HV, Polach SA, Wang Z (2000) Coinage metal complexes of 3,5-bis(trifluoromethyl)pyrazolate ligand: synthesis and characterization of {[3,5-(CF3)2Pz]Cu}3 and {[3,5-(CF3)2Pz]Ag}3. J Fluor Chem 103(2):163–169

    Article  Google Scholar 

  14. Dias HVR, Diyabalanage HVK, Eldabaja MG, Elbjeirami O, Rawashdeh-Omary MA, Omary MA (2005) Brightly phosphorescent trinuclear copper(I) complexes of pyrazolates: substituent effects on the supramolecular structure and photophysics. J Am Chem Soc 127(20):7489–7501

    Article  CAS  Google Scholar 

  15. Dias HVR, Gamage CSP, Keltner J, Diyabalanage HVK, Omari I, Eyobo Y, Dias NR, Roehr N, McKinney L, Poth T (2007) Trinuclear silver(I) complexes of fluorinated pyrazolates. Inorg Chem 46(8):2979–2987

    Article  CAS  Google Scholar 

  16. Titov AA, Filippov OA, Bilyachenko AN, Smol’yakov AF, Dolgushin FM, Belsky VK, Godovikov IA, Epstein LM, Shubina ES (2012) Complexes of trinuclear macrocyclic copper(I) and silver(I) 3,5-bis(trifluoromethyl)pyrazolates with ketones. Eur J Inorg Chem 33:5554–5561

    Article  Google Scholar 

  17. Tsupreva VN, Titov AA, Filippov OA, Bilyachenko AN, Smol’yakov AF, Dolgushin FM, Agapkin DV, Godovikov IA, Epstein LM, Shubina ES (2011) Peculiarities of the complexation of copper and silver adducts of a 3,5-bis(trifluoromethyl)pyrazolate ligand with organoiron compounds. Inorg Chem 50(8):3325–3331

    Article  CAS  Google Scholar 

  18. Titov AA, Smol’yakov AF, Filippov OA, Godovikov IA, Muratov DA, Dolgushin FM, Epstein LM, Shubina ES (2017) Supramolecular design of the trinuclear silver(I) and copper(I) metal pyrazolates complexes with ruthenium sandwich compounds via intermolecular metal–π interactions. Cryst Growth Des 17(12):6770–6779

    Article  CAS  Google Scholar 

  19. Sheldrick G (2015) Crystal structure refinement with SHELXL. Acta Crystallogr C 71(1):3–8

    Article  Google Scholar 

  20. Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H (2009) OLEX2: a complete structure solution, refinement and analysis program. J Appl Cryst 42(2):339–341

    Article  CAS  Google Scholar 

  21. Shimoni L, Glusker JP (1994) The geometry of intermolecular interactions in some crystalline fluorine-containing organic compounds. Struct Chem 5(6):383–397

    Article  CAS  Google Scholar 

  22. Bondi A (1964) van der Waals volumes and radii. J Phys Chem 68(3):441–451

    Article  CAS  Google Scholar 

  23. Li L-L, Feng X-Q, Han R-P, Zang S-Q, Yang G (2017) Cr(VI) removal via anion exchange on a silver-triazolate MOF. J Hazard Mater 321:622–628

    Article  Google Scholar 

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Acknowledgements

This work has been supported by the National Natural Science Foundation of China (Grant No. 21471132) and China Postdoctoral Science Foundation (Grant No. 2018M642770).

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Authors and Affiliations

  1. College of Chemistry, Zhengzhou University, Zhengzhou, 450001, People’s Republic of China

    Rongrong Liu, Jing-Huo Chen, Guang Yang & Wenhua Zhang

  2. School of Basic Medical Sciences, Xinxiang Medical College, Xinxiang, 453003, People’s Republic of China

    Pingning Jin

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  1. Rongrong Liu
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  2. Pingning Jin
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  3. Jing-Huo Chen
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  4. Guang Yang
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  5. Wenhua Zhang
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Correspondence to Wenhua Zhang.

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Liu, R., Jin, P., Chen, JH. et al. A green approach to the preparation of triangular silver(I) 3,5-bis(trifluoromethyl)pyrazolate: crystal structures of two adducts with triethylammonium nitrate or benzoic acid. Transit Met Chem 44, 755–761 (2019). https://doi.org/10.1007/s11243-019-00345-z

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