Cerium(iii) complexes with azolyl-substituted thiophenolate ligands: synthesis,structure and red luminescence |
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| Authors: | Vasily A. Ilichev Liubov I. Silantyeva Ivan D. Grishin Anton V. Rozhkov Roman V. Rumyantcev Georgy K. Fukin Mikhail N. Bochkarev |
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| Affiliation: | G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod Russian Federation.; Nizhny Novgorod State University, Gagarina Avenue 23/2, 603950 Nizhny Novgorod Russian Federation ; Saint Petersburg State University, Universitetskaya Emb. 7/9, 199034 St Petersburg Russian Federation |
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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.Novel Ce(iii) complexes with azolyl-substituted thiolate ligands have been synthesized. Some of them exhibit red PL. |
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