Tl2[B10H10] und Tl2[B12H12]: Kristallstrukturen, Raman-Spektren und Tl+-Lone-Pair-Lumineszenz im Vergleich

Kevin U. Bareiß; Fabian M. Kleeberg; David Enseling; Thomas Jüstel; Thomas Schleid

doi:10.1515/znb-2022-0007

Published by De Gruyter February 21, 2022

Tl₂[B₁₀H₁₀] und Tl₂[B₁₂H₁₂]: Kristallstrukturen, Raman-Spektren und Tl⁺-Lone-Pair-Lumineszenz im Vergleich

Tl₂[B₁₀H₁₀] and Tl₂[B₁₂H₁₂]: crystal structures, Raman spectra and Tl⁺ lone-pair luminescence in comparison

Kevin U. Bareiß , Fabian M. Kleeberg , David Enseling , Thomas Jüstel and Thomas Schleid

From the journal Zeitschrift für Naturforschung B

https://doi.org/10.1515/znb-2022-0007

Showing a limited preview of this publication:

Abstract

Thallium(I) decahydro-closo-decaborate Tl₂[B₁₀H₁₀] and thallium(I) dodecahydro-closo-dodecaborate Tl₂[B₁₂H₁₂] are readily available as microcrystalline powders from reactions of thallium(I) carbonate Tl₂[CO₃] with aqueous solutions of the respective free acid (H₃O)₂[B₁₀H₁₀] or (H₃O)₂[B₁₂H₁₂]. Tl₂[B₁₂H₁₂] crystallizes with an anti-fluorite related structure (cubic, Fm3‾, a = 1074.23(8) pm, Z = 4). Each Tl⁺ cation is coordinated by four icosahedral [B₁₂H₁₂]^2– anions (d(B–B) = 180–181 pm) providing a twelvefold coordination sphere of hydrogen atoms (d(Tl–H) = 296 pm). Tl₂[B₁₀H₁₀] crystallizes monoclinically in the space group P2₁/n with a = 704.03(5), b = 1111.45(8), c = 1281.16(9) pm and β = 94.912(3)° for Z = 4. The bicapped square antiprismatic [B₁₀H₁₀]^2– anions (d(B–B) = 147–176 pm to the two apical boron atoms, d(B–B) = 161–199 pm within the corpus) again form distorted tetrahedra around the (Tl1)⁺, but square pyramids around the (Tl2)⁺ cations. Thus (Tl1)⁺ is coordinated by 12 hydrogen atoms (d(Tl1–H) = 275–315 pm), but (Tl2)⁺ only by 11 of them (d(Tl2–H) = 267–357 pm). Both compounds show a greenish-yellow photoluminescence caused by an interconfigurational 6sp–6s² emission (³P_n→¹S₀, n = 0–2) at the Tl⁺ cation.

Keywords: decahydro-closo-decaborates; dodecahydro-closo-dodecaborates; lone-pair cations; Raman and photoluminescence spectroscopy; thallium

Professor Holger Braunschweig zum 60. Geburtstag gewidmet.

Corresponding author: Thomas Schleid, Universität Stuttgart, Stuttgart, Germany, E-mail: thomas.schleid@iac.uni-stuttgart.de

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

Literatur

1. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2001, 627, 1836–1845; https://doi.org/10.1002/1521-3749(200108)627:8<1836::aid-zaac1836>3.0.co;2-a.10.1002/1521-3749(200108)627:8<1836::AID-ZAAC1836>3.0.CO;2-ASearch in Google Scholar

2. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2004, 630, 541–546; https://doi.org/10.1002/zaac.200300416.Search in Google Scholar

3. Van, Ng.-D., Kleeberg, F. M., Schleid, Th. Z. Anorg. Allg. Chem. 2015, 641, 2484–2489; https://doi.org/10.1002/zaac.201500572.Search in Google Scholar

4. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2008, 634, 317–324; https://doi.org/10.1002/zaac.200700399.Search in Google Scholar

5. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2005, 631, 1593–1596; https://doi.org/10.1002/zaac.200500093.Search in Google Scholar

6. Tiritiris, I. Untersuchungen zu Reaktivität, Aufbau und struktureller Dynamik von salzartigen closo-Dodekaboraten. Dissertation, Universität Stuttgart, Stuttgart, 2004.Search in Google Scholar

7. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2002, 628, 1411–1418; https://doi.org/10.1002/1521-3749(200206)628:6<1411::aid-zaac1411>3.0.co;2-x.10.1002/1521-3749(200206)628:6<1411::AID-ZAAC1411>3.0.CO;2-XSearch in Google Scholar

8. Yousufuddin, M., Her, J.-H., Zhou, W., Jalisatgi, S. S., Udovic, T. J. Inorg. Chim. Acta. 2009, 362, 3155–3158; https://doi.org/10.1016/j.ica.2009.02.020.Search in Google Scholar

9. Ponomarev, V. I., Lyubeznova, T. Y., Solntsev, K. A., Kuznetsov, N. T. Koord. Khim. 1991, 17, 21–27.Search in Google Scholar

10. Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2003, 629, 1390–1402; https://doi.org/10.1002/zaac.200300098.Search in Google Scholar

11. Tiritiris, I., Schleid, Th., Müller, K., Preetz, W. Z. Anorg. Allg. Chem. 2000, 626, 323–325; https://doi.org/10.1002/(sici)1521-3749(200002)626:2<323::aid-zaac323>3.0.co;2-q.10.1002/(SICI)1521-3749(200002)626:2<323::AID-ZAAC323>3.0.CO;2-QSearch in Google Scholar

12. Tiritiris, I., Van, Ng.-D., Schleid, Th. Z. Anorg. Allg. Chem. 2011, 637, 682–688; https://doi.org/10.1002/zaac.201000457.Search in Google Scholar

13. Kleeberg, F. M., Zimmermann, L. W., Schleid, Th. J. Cluster Sci. 2022, 33; https://doi.org/10.1007/s10876-021-02166-6.Search in Google Scholar

14. Zimmermann, L. W., Van, Ng.-D., Gudat, D., Schleid, Th. Angew. Chem. Int. Ed. 2016, 128, 1942–1945; https://doi.org/10.1002/ange.201509629.Search in Google Scholar

15. Kleeberg, F. M. Synthese und Strukturaufklärung neuer salzartiger Dekahydro-closo-Dekaborate und Dodekahydro-closo-Dodekaborate sowie deren halogenierter Derivate. Dissertation, Universität Stuttgart, Stuttgart, 2017.Search in Google Scholar

16. Knoth, W. H., Miller, H. C., Sauer, J. C., Balthis, J. H., Chia, Y. T., Muetterties, E. L. Inorg. Chem. 1964, 3, 159–167; https://doi.org/10.1021/ic50012a002.Search in Google Scholar

17. Kunkely, H., Vogler, A. Inorg. Chim. Acta. 2007, 360, 679–680; https://doi.org/10.1016/j.ica.2006.08.059.Search in Google Scholar

18. Dobrott, R. D., Lipscomb, W. N. J. Chem. Phys. 1962, 37, 1779–1784; https://doi.org/10.1063/1.1733368.Search in Google Scholar

19. Hofmann, K., Albert, B. Z. Kristallogr. 2005, 220, 142–146; https://doi.org/10.1524/zkri.220.2.142.59144.Search in Google Scholar

20. Otwinowski, Z., Minor, W. Methods Enzymol. 1997, 276, 307–326; https://doi.org/10.1016/s0076-6879(97)76066-x.Search in Google Scholar

21. Stoe & Cie. X-RED32 (version 1.31); Stoe & Cie: Darmstadt, Germany, 2005.Search in Google Scholar

22. Sheldrick, G. M. SHELXS/L-97, Programs for Crystal Structure Determination; University of Göttingen: Göttingen, 1997.Search in Google Scholar

23. Osram Sylvania Color Calculator 7.77, downloaded December 2021. https://www.osram.us/cb/tools-and-resources/applications/led-colorcalculator/index.jsp.Search in Google Scholar

24. Shannon, R. D. Acta Crystallogr. 1976, A32, 751–767; https://doi.org/10.1107/s0567739476001551.Search in Google Scholar

25. Van, Ng.-D., Tiritiris, I., Schleid, Th. Z. Anorg. Allg. Chem. 2004, 630, 1764; https://doi.org/10.1002/zaac.200470140.Search in Google Scholar

26. Muetterties, E. L., Merrifield, R. E., Miller, H. C., Knoth, W. H., Downing, J. R. J. Am. Chem. Soc. 1962, 84, 2506–2508; https://doi.org/10.1021/ja00872a011.Search in Google Scholar

27. Weber, W., Thorpe, M. F. J. Phys. Chem. Solid. 1975, 36, 967–974; https://doi.org/10.1016/0022-3697(75)90176-6.Search in Google Scholar

28. Abdul-Fattah, M., Butler, I. Canad. J. Spectrosc. 1977, 22, 110–112.Search in Google Scholar

29. Boyle, L. L., Parker, Y. M. Mol. Phys. 1980, 39, 95–109; https://doi.org/10.1080/00268978000100091.Search in Google Scholar

30. Leites, L. A., Bukalov, S. S., Kurbakova, A. P., Kaganski, M. M., Gaft, Y., Kuznetsov, N. T., Zakharova, I. A. Spectrochim. Acta 1982, 38A, 1047–1056; https://doi.org/10.1016/0584-8539(82)80032-9.Search in Google Scholar

31. Leites, L. A., Kurbakova, A. P., Kaganskii, M. M., Gaft, Y. L., Zakharova, I. A., Kuznetsov, N. T. Izvest. Akad. Nauk SSSR Ser. Khim. 1983, 10, 2284–2292.Search in Google Scholar

32. Tiritiris, I., Weidlein, J., Schleid, Th. Z. Naturforsch. 2005, 60b, 627–639; https://doi.org/10.1515/znb-2005-0605.Search in Google Scholar

33. Preetz, W., Srebny, H.-G. Z. Naturforsch. 1984, 39b, 6–13; https://doi.org/10.1515/znb-1984-0103.Search in Google Scholar

34. Weidlein, J., Müller, U., Dehnicke, K. Schwingungsspektroskopie; Thieme-Verlag: Stuttgart, 1988; pp. S. 142–144.Search in Google Scholar

35. Blasse, G., Grabmeier, B. C. Luminescent Materials; Springer-Verlag: Berlin, Heidelberg, New York, 1994.10.1007/978-3-642-79017-1Search in Google Scholar

36. Seitz, F. J. Chem. Phys. 1938, 6, 150–162; https://doi.org/10.1063/1.1750216.Search in Google Scholar

37. Nagy, R., Wollentin, R. W., Lui, C. K. J. Electrochem. Soc. 1950, 97, 29–32; https://doi.org/10.1149/1.2777961.Search in Google Scholar

38. Yen, W. M., Shionoya, S., Yamamoto, H. Phosphor Handbook; CRC Press: Boca Raton, London, New York, 2007.10.1201/9781420005233Search in Google Scholar

39. Brauer, P., Aberle, N., Knothe, M. Z. Naturforsch. 1967, 22a, 2059–2066; https://doi.org/10.1515/zna-1967-1231.Search in Google Scholar

40. Clapp, R. H., Ginther, R. J. J. Opt. Soc. Am. 1947, 37, 355–362; https://doi.org/10.1364/josa.37.000355.Search in Google Scholar PubMed

41. Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112–122; https://doi.org/10.1107/s0108767307043930.Search in Google Scholar

Erhalten: 2022-01-13

Angenommen: 2022-01-23

Online erschienen: 2022-02-21

Erschienen im Druck: 2022-03-28

Tl₂[B₁₀H₁₀] und Tl₂[B₁₂H₁₂]: Kristallstrukturen, Raman-Spektren und Tl⁺-Lone-Pair-Lumineszenz im Vergleich

Abstract

Literatur

Journal and Issue

Articles in the same Issue