Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>]
Tl[CB<sub>11</sub>H<sub>12</sub>] was prepared with a reaction of Tl<sub>2</sub>[CO<sub>3</sub>] with the acid of the monocarba-<i>closo</i>-dodecaborate anion (H<sub>3</sub>O)[CB<sub>11</sub>H<sub>12</sub&g...
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MDPI AG
2022-12-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/12/12/1840 |
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| author | Kevin U. Bareiß David Enseling Thomas Jüstel Thomas Schleid |
| author_facet | Kevin U. Bareiß David Enseling Thomas Jüstel Thomas Schleid |
| author_sort | Kevin U. Bareiß |
| collection | DOAJ |
| description | Tl[CB<sub>11</sub>H<sub>12</sub>] was prepared with a reaction of Tl<sub>2</sub>[CO<sub>3</sub>] with the acid of the monocarba-<i>closo</i>-dodecaborate anion (H<sub>3</sub>O)[CB<sub>11</sub>H<sub>12</sub>] in aqueous solution as prismatic colorless single crystals by isothermal evaporation from the clear brine. It crystallizes in a monoclinic primitive structure with the space group <i>P</i>2<sub>1</sub>/<i>c</i> (<i>a</i> = 685.64(3) pm, <i>b</i> = 1978.21(9) pm, <i>c</i> = 1006.89(5) pm, <i>β</i> = 132.918(3)° for <i>Z</i> = 4), which can be derived from the halite-type arrangement if the <i>closo</i>-carbaborate cages are considered as spheres. Due to the different atoms in the [CB<sub>11</sub>H<sub>12</sub>]<sup>−</sup> anion, Tl[CB<sub>11</sub>H<sub>12</sub>] features interesting C–H<sup>δ+</sup> ∙∙∙ <sup>δ−</sup>H–B interactions near to non-classical hydrogen bridges (“dihydrogen bonds”) and exhibits considerably different luminescence properties compared to regular <i>closo</i>-hydroborates, such as Tl<sub>2</sub>[B<sub>10</sub>H<sub>10</sub>], Tl<sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] and Tl<sub>3</sub>Cl[B<sub>12</sub>H<sub>12</sub>]. Tl[CB<sub>11</sub>H<sub>12</sub>] shows strong photoluminescence (PL) at 390 nm, while the excitation bands for this broad band are located at 245 and 280 nm. It is caused by an interconfigurational [Xe]4f<sup>14</sup>5d<sup>10</sup>6s<sup>2</sup> (<sup>3</sup>P<sub>1</sub>) to [Xe]4f<sup>14</sup>5d<sup>10</sup>6s<sup>1</sup>6p<sup>1</sup> (<sup>1</sup>S<sub>0</sub>) transition, which is also known as lone-pair luminescence. The quantum yield is rather low (<10 %), which is likely caused by the rather large Stokes shift. In addition, temperature-dependent emission spectra were recorded to determine the thermal quenching curve and the respective quenching temperature. |
| first_indexed | 2024-03-09T17:09:20Z |
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| last_indexed | 2024-03-09T17:09:20Z |
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| spelling | doaj.art-6a6c924b654a4d718132ee87fa619e532023-11-24T14:11:54ZengMDPI AGCrystals2073-43522022-12-011212184010.3390/cryst12121840Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>]Kevin U. Bareiß0David Enseling1Thomas Jüstel2Thomas Schleid3Institute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyDepartment of Chemical Engineering, FH Münster—University of Applied Sciences, Stegerwaldstraße 39, 48565 Steinfurt, GermanyDepartment of Chemical Engineering, FH Münster—University of Applied Sciences, Stegerwaldstraße 39, 48565 Steinfurt, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyTl[CB<sub>11</sub>H<sub>12</sub>] was prepared with a reaction of Tl<sub>2</sub>[CO<sub>3</sub>] with the acid of the monocarba-<i>closo</i>-dodecaborate anion (H<sub>3</sub>O)[CB<sub>11</sub>H<sub>12</sub>] in aqueous solution as prismatic colorless single crystals by isothermal evaporation from the clear brine. It crystallizes in a monoclinic primitive structure with the space group <i>P</i>2<sub>1</sub>/<i>c</i> (<i>a</i> = 685.64(3) pm, <i>b</i> = 1978.21(9) pm, <i>c</i> = 1006.89(5) pm, <i>β</i> = 132.918(3)° for <i>Z</i> = 4), which can be derived from the halite-type arrangement if the <i>closo</i>-carbaborate cages are considered as spheres. Due to the different atoms in the [CB<sub>11</sub>H<sub>12</sub>]<sup>−</sup> anion, Tl[CB<sub>11</sub>H<sub>12</sub>] features interesting C–H<sup>δ+</sup> ∙∙∙ <sup>δ−</sup>H–B interactions near to non-classical hydrogen bridges (“dihydrogen bonds”) and exhibits considerably different luminescence properties compared to regular <i>closo</i>-hydroborates, such as Tl<sub>2</sub>[B<sub>10</sub>H<sub>10</sub>], Tl<sub>2</sub>[B<sub>12</sub>H<sub>12</sub>] and Tl<sub>3</sub>Cl[B<sub>12</sub>H<sub>12</sub>]. Tl[CB<sub>11</sub>H<sub>12</sub>] shows strong photoluminescence (PL) at 390 nm, while the excitation bands for this broad band are located at 245 and 280 nm. It is caused by an interconfigurational [Xe]4f<sup>14</sup>5d<sup>10</sup>6s<sup>2</sup> (<sup>3</sup>P<sub>1</sub>) to [Xe]4f<sup>14</sup>5d<sup>10</sup>6s<sup>1</sup>6p<sup>1</sup> (<sup>1</sup>S<sub>0</sub>) transition, which is also known as lone-pair luminescence. The quantum yield is rather low (<10 %), which is likely caused by the rather large Stokes shift. In addition, temperature-dependent emission spectra were recorded to determine the thermal quenching curve and the respective quenching temperature.https://www.mdpi.com/2073-4352/12/12/1840carboratesthallium(I) saltsmonocarba-<i>closo</i>-hydroboratessingle-crystal X-ray diffractionRaman spectraphotoluminescence |
| spellingShingle | Kevin U. Bareiß David Enseling Thomas Jüstel Thomas Schleid Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] Crystals carborates thallium(I) salts monocarba-<i>closo</i>-hydroborates single-crystal X-ray diffraction Raman spectra photoluminescence |
| title | Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] |
| title_full | Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] |
| title_fullStr | Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] |
| title_full_unstemmed | Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] |
| title_short | Crystal Structure, Raman Spectrum and Tl<sup>+</sup> Lone-Pair Luminescence of Thallium(I) Dodecahydro-Monocarba-<i>closo</i>-Dodecaborate Tl[CB<sub>11</sub>H<sub>12</sub>] |
| title_sort | crystal structure raman spectrum and tl sup sup lone pair luminescence of thallium i dodecahydro monocarba i closo i dodecaborate tl cb sub 11 sub h sub 12 sub |
| topic | carborates thallium(I) salts monocarba-<i>closo</i>-hydroborates single-crystal X-ray diffraction Raman spectra photoluminescence |
| url | https://www.mdpi.com/2073-4352/12/12/1840 |
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