Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence

Vasily A. Ilichev, Liubov I. Silantyeva, Ivan D. Grishin, Anton V. Rozhkov, Roman V. Rumyantcev, Georgy K. Fukin, Mikhail N. Bochkarev

Research output

Abstract

In order to obtain molecular Ce(iii) complexes which emit red light by f-d transitions the azolyl-substituted thiophenolates were used as the ligands. The thiophenolate Ce(iii) complexes were synthesized by the reaction of Ce[N(SiMe3)2]3 with respective thiophenols 2-(2′-mercaptophenyl)benzimidazole (H(NSN)), 2-(2′-mercaptophenyl)benzoxazole (H(OSN)) and 2-(2′-mercaptophenyl)benzothiazole (H(SSN)) in DME media. The structures of the benzimidazolate (Ce(NSN)3(DME)) and benzothiazolate (Ce(SSN)3(DME)) derivatives were determined by X-ray analysis which revealed that the cerium ion in the molecules is coordinated by one DME and three anionic thiophenolate ligands. The lanthanum complex La(OSN)3(DME) has been synthesized similarly and structurally characterized. It was found that the solids of Ce(SSN)3(DME) and Ce(OSN)3(DME) exhibit a broad band photoluminescence peaking at 620 nm which disappears upon solvatation. With an example of OSN derivatives it was proposed that this behaviour is caused by the blue shift of the f-d transition of Ce3+ ions.

Original languageEnglish
Pages (from-to)24110-24116
Number of pages7
JournalRSC Advances
Volume9
Issue number42
DOIs
Publication statusPublished - 30 Jul 2019

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Cerium
Luminescence
Benzoxazoles
Ligands
Ions
Derivatives
Lanthanum
X ray analysis
Photoluminescence
Molecules
benzimidazole
benzothiazole
thiophenol

Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Ilichev, V. A., Silantyeva, L. I., Grishin, I. D., Rozhkov, A. V., Rumyantcev, R. V., Fukin, G. K., & Bochkarev, M. N. (2019). Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence. RSC Advances, 9(42), 24110-24116. https://doi.org/10.1039/c9ra03199e
Ilichev, Vasily A. ; Silantyeva, Liubov I. ; Grishin, Ivan D. ; Rozhkov, Anton V. ; Rumyantcev, Roman V. ; Fukin, Georgy K. ; Bochkarev, Mikhail N. / Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence. In: RSC Advances. 2019 ; Vol. 9, No. 42. pp. 24110-24116.
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abstract = "In order to obtain molecular Ce(iii) complexes which emit red light by f-d transitions the azolyl-substituted thiophenolates were used as the ligands. The thiophenolate Ce(iii) complexes were synthesized by the reaction of Ce[N(SiMe3)2]3 with respective thiophenols 2-(2′-mercaptophenyl)benzimidazole (H(NSN)), 2-(2′-mercaptophenyl)benzoxazole (H(OSN)) and 2-(2′-mercaptophenyl)benzothiazole (H(SSN)) in DME media. The structures of the benzimidazolate (Ce(NSN)3(DME)) and benzothiazolate (Ce(SSN)3(DME)) derivatives were determined by X-ray analysis which revealed that the cerium ion in the molecules is coordinated by one DME and three anionic thiophenolate ligands. The lanthanum complex La(OSN)3(DME) has been synthesized similarly and structurally characterized. It was found that the solids of Ce(SSN)3(DME) and Ce(OSN)3(DME) exhibit a broad band photoluminescence peaking at 620 nm which disappears upon solvatation. With an example of OSN derivatives it was proposed that this behaviour is caused by the blue shift of the f-d transition of Ce3+ ions.",
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Ilichev, VA, Silantyeva, LI, Grishin, ID, Rozhkov, AV, Rumyantcev, RV, Fukin, GK & Bochkarev, MN 2019, 'Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence', RSC Advances, vol. 9, no. 42, pp. 24110-24116. https://doi.org/10.1039/c9ra03199e

Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence. / Ilichev, Vasily A.; Silantyeva, Liubov I.; Grishin, Ivan D.; Rozhkov, Anton V.; Rumyantcev, Roman V.; Fukin, Georgy K.; Bochkarev, Mikhail N.

In: RSC Advances, Vol. 9, No. 42, 30.07.2019, p. 24110-24116.

Research output

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T1 - Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: Synthesis, structure and red luminescence

AU - Ilichev, Vasily A.

AU - Silantyeva, Liubov I.

AU - Grishin, Ivan D.

AU - Rozhkov, Anton V.

AU - Rumyantcev, Roman V.

AU - Fukin, Georgy K.

AU - Bochkarev, Mikhail N.

PY - 2019/7/30

Y1 - 2019/7/30

N2 - In order to obtain molecular Ce(iii) complexes which emit red light by f-d transitions the azolyl-substituted thiophenolates were used as the ligands. The thiophenolate Ce(iii) complexes were synthesized by the reaction of Ce[N(SiMe3)2]3 with respective thiophenols 2-(2′-mercaptophenyl)benzimidazole (H(NSN)), 2-(2′-mercaptophenyl)benzoxazole (H(OSN)) and 2-(2′-mercaptophenyl)benzothiazole (H(SSN)) in DME media. The structures of the benzimidazolate (Ce(NSN)3(DME)) and benzothiazolate (Ce(SSN)3(DME)) derivatives were determined by X-ray analysis which revealed that the cerium ion in the molecules is coordinated by one DME and three anionic thiophenolate ligands. The lanthanum complex La(OSN)3(DME) has been synthesized similarly and structurally characterized. It was found that the solids of Ce(SSN)3(DME) and Ce(OSN)3(DME) exhibit a broad band photoluminescence peaking at 620 nm which disappears upon solvatation. With an example of OSN derivatives it was proposed that this behaviour is caused by the blue shift of the f-d transition of Ce3+ ions.

AB - In order to obtain molecular Ce(iii) complexes which emit red light by f-d transitions the azolyl-substituted thiophenolates were used as the ligands. The thiophenolate Ce(iii) complexes were synthesized by the reaction of Ce[N(SiMe3)2]3 with respective thiophenols 2-(2′-mercaptophenyl)benzimidazole (H(NSN)), 2-(2′-mercaptophenyl)benzoxazole (H(OSN)) and 2-(2′-mercaptophenyl)benzothiazole (H(SSN)) in DME media. The structures of the benzimidazolate (Ce(NSN)3(DME)) and benzothiazolate (Ce(SSN)3(DME)) derivatives were determined by X-ray analysis which revealed that the cerium ion in the molecules is coordinated by one DME and three anionic thiophenolate ligands. The lanthanum complex La(OSN)3(DME) has been synthesized similarly and structurally characterized. It was found that the solids of Ce(SSN)3(DME) and Ce(OSN)3(DME) exhibit a broad band photoluminescence peaking at 620 nm which disappears upon solvatation. With an example of OSN derivatives it was proposed that this behaviour is caused by the blue shift of the f-d transition of Ce3+ ions.

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U2 - 10.1039/c9ra03199e

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