Tetrathiafulvalene mono- and bis-1,2,3-triazole precursors by click chemistry: structural diversity and reactivity

Abstract

The donor ortho-dimethyl-TTF-(N-n-Bu-1,2,3-triazole) 1,5-isomer has been synthesized by click chemistry following a ruthenium-catalyzed azide-alkyne cycloaddition procedure. The single crystal X-ray analysis showed a planar conformation between the TTF and triazole units and a set of intermolecular interactions at the supramolecular level in the solid state. The same procedure allowed the preparation of the corresponding ortho-dimethyl-TTF-bis(triazole) which was also structurally characterized. Because of the steric hindrance, the triazole units are no longer planar with the TTF backbone. The reactivity of the triazole ring has been investigated in protonation and alkylation reactions, monitored by UV-visible spectroscopy, which clearly showed the red shift of the intramolecular charge transfer band. A TTF-methyl-triazolium salt has been isolated and analyzed by single crystal X-ray analysis. All of the TTF-triazoles and triazolium salts are valuable precursors for radical cation salts due to their oxidation potentials and variety of possible intermolecular interactions.

Ruthenium-Catalyzed Azide Alkyne Cycloaddition Reaction: Scope, Mechanism, and Applications

“…Interestingly, despite their similarities, these compounds crystallize in a different fashion, where 150 forms head-to-tail dimers while 153 is arranged in columns with each unit slightly shifted in comparison to the molecule above and below so that the TTFmoiety stacks with a triazole unit directly above. The effect of protonation and alkylation of the triazole ring in 149 was also studied, 256 Figure 32. Triazole-containing tetrathiafulvalenes (TTFs) [254][255][256] Lumpi has also applied the alkyne-azide cycloaddition as a means to prepare new molecular materials, in this case nonlinear optic materials (NLOs) derived from a central enyne scaffold.…”

“…The effect of protonation and alkylation of the triazole ring in 149 was also studied, 256 Figure 32. Triazole-containing tetrathiafulvalenes (TTFs) [254][255][256] Lumpi has also applied the alkyne-azide cycloaddition as a means to prepare new molecular materials, in this case nonlinear optic materials (NLOs) derived from a central enyne scaffold. 257 The majority of structures were formed using CuAAC, but one compound was prepared via microwave-assisted RuAAC using [Cp*RuCl] 4 as the catalyst (Scheme 59).…”

“…In a series of reports, Avarvari has investigated the structures and properties of a TTF-scaffold functionalized with 1,5-disubstitued triazole units. [254][255][256] Employing a tetrathiafulvalene with one or two appended alkyne units, compounds 149-154…”

Covalent non-fused tetrathiafulvalene–acceptor systems

“…63 In compound 35, the benzyl substituent was replaced by n-butyl by using butyl azide, while the bis(Trz) derivative 36 was obtained starting from TTF-bis(alkyne). 64 The chelating ligands Py-Trz 37 and Py(Trz) 2 38 were prepared from the corresponding pyridine azides by the same Ru(II)-based cycloaddition strategy. 65 The attachment position of TTF to the triazole ring is important, making the 1,4-isomers easier to oxidize than the 1,5-isomers (Table 4).…”

Progress on Synthesis and Application of Triazole-Based Tetrathiafulvalene Derivatives

“…1), 并广 泛应用于生物耦合 [21] 、药物设计 [22] 、高分子合成 [23] 、超 分子 [24] 和材料化学 [25] 等领域. [27] , 质子化 6 的 紫外光谱红移更明显. 为考察功能取代基的影响, 同年, 该课题组利用 RuAAC 点击反应合成了含吡啶功能基的 TTF 衍生物 8 和 9 (Scheme 2) [28] .…”