Novel ditopic 2-mercaptothiazoles and their sodium salts: synthesis, structural diversity and luminescence. (6th July 2022)

• Record Type: Journal Article
• Authors: Rogozhin, Anton F.; Ilichev, Vasily A.; Fagin, Anatoly A.; Rumyantcev, Roman V.; Fukin, Georgy K.; Yablonskiy, Artem N.; Andreev, Boris A.; Bochkarev, Mikhail N.
• Is Part Of: New journal of chemistry. Volume 46:Number 29(2022)
• Page Start: 13987
• Page End: 13995
• Publication Date: 2022-07-06
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d2nj02746a
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : A set of novel ditopic 2-mercaptothiazoles has been synthesized. Depending on the nature of the bisthiazoles their sodium salts can form coordination compounds or 2D polymers. Abstract : A set of novel bis-(2-mercaptothiazoles) has been synthesized. 4, 5-Difluorobenzo[1, 2- d :3, 4- d ′]bisthiazole-2, 7-dithiol (1 ), 4, 8-difluorobenzo[1, 2- d :5, 4- d ′]bisthiazole-2, 6-dithiol (2 ), 4, 4′, 5, 5′, 7, 7′-hexafluoro-[6, 6′-bibenzo[d]thiazole]-2, 2′-dithiol (3 ) and naphtho[1, 2- d :5, 6- d ′]bis(thiazole)-2, 7-dithiol (4 ) were obtained by condensation of halogenated aromatic diamines or dinitro compounds with potassium ethylxanthate or CS2 while the synthesis of benzo[1, 2- d :4, 5- d ′]bis(thiazole)-2, 6-dithiol (5 ) was performed starting from a centrosymmetric benzodiaminedithiol. The disodium salts of new bisthiazoles 1–5 as well as previously known benzo[1, 2- d :5, 4- d ′]bisthiazole-2, 6-dithiol (H2 (dmbt)) with a formula Na2 L x (DME)4 (L = 1–3, 5, dmbt) were synthesized from sodium sylilamide NaN(SiMe3 )2 and respective bisthizoles in DME media. X-Ray srtuctural analysis revealed that the salts of bisthiazoles 2, 5 and dmbt are molecular complexes in which bisthiazoles act as ditopic ligands coordinating two sodium atoms. A similar reaction of 4 and NaN(SiMe3 )2 in DME media results in a formation of 2D coordination polymer [Na2 L 4 (DME)2 ] n which shows an intense photoluminescence (PL) at room temperature and 77 K. Solvent replacement in [Na2 L 4 (DME)2 ] n with THF results in a formation of novel 2D coordination polymer [Na2 L 4 (THF)4 ] n which turned out to be non-luminescent. Time-resolved PL spectroscopy revealed that the low temperature PL of the disodium salts consists of fluorescent and phosporescent components. Based on the phosphorescence spectra the triplet levels of the bisthizoles were found to be 21 400, 21 400, 21 500, 21 600, 18 900 and 21 200 cm −1 for bithiazoles 1–5 and dmbt respectively.