The Synthesis of Covalent Triazine‐Based Frameworks via Friedel–Crafts Reactions of Cyanuric Chloride with Thienyl and Carbazolyl Derivatives for Fluorescence Sensing to Picric Acid, Iodine and Capturing Iodine

Abstract

A multifunctional thiophene-based covalent triazine framework (TTPATTh) with triphenylamine as core is synthesized by Friedel-Crafts reaction of cyanuric chloride with thienyl derivative for the first time. The yield of TTPATTh (99.59%) is far higher than that of the carbazole-based CTF (TTPATCz, 47.03%). TTPATTh and TTPATCz possess high BET surface areas with 1235 and 2501 m 2 g -1 as well as high pore volumes with 1.60 and 2.23 cm 3 g -1 , respectively. TTPATTh and TTPATCz have high thermal stability with high thermal decomposition temperatures of 514 and 598 °C in nitrogen atmosphere. With the introduction of triazine rings, the fluorescence sensing sensitivities of TTPATTh and TTPATCz to picric acid and iodine are improved significantly. Especially for TTPATTh, the K sv values reach 5.95 × 10 5 and 1.61 × 10 4 L mol -1 , and LODs reach 1.02 × 10 -12 and 1.86 × 10 -12 mol L -1 . To the best of the knowledge, this is the most sensitive value among thiophene-based porous organic polymers to PA and I 2 . Furthermore, TTPATTh and TTPATCz can also adsorb iodine in vapor phase, cyclohexane solution and aqueous solution, and release iodine by heating or in ethanol solution. The efficiency of controlling the release of iodine is higher than that in ethanol.

Recent advances in the design, synthesis and catalytic applications of triazine-based covalent organic polymers

“…The BET surface area and pore volume were found Scheme 10 Schematics for the synthesis of TTPATTh and TTPATCz. 54 to be 481.1 m 2 g À1 and 0.710 cc g À1 , respectively. Morphological studies show a regular spherical morphology, which was obtained as a result of cross edge-to-edge interaction of precursors.…”

“…Very recently in 2021, Tong et al reported two multifunctional COPs named as TTPATTh and TPATCz triazine-thiophene-based polymeric materials through the Friedel-Crafts polymerization of cyanuric chloride with TPATTh (tris[4-(2-thienyl)phenyl]amine) and TPATC (tris[4-carbazoyl-9-ylphenyl]amine). 54 This report presents an effective application of Friedel-Crafts arylation reaction using methanesulfonic acid (CH 3 SO 3 H) as the catalyst to synthesize a thiophene-fused covalent triazine polymeric network (Scheme 10). The reaction of cyanuric chloride with TPATTh yielded TTPATTh (99.59%), which is far more than that of TPATCz (TTPATCz, 47.03%).…”

“…Scheme 10 Schematics for the synthesis of TTPATTh and TTPATCz 54. (Reproduced from ref 54. with permission from the John Wiley and Sons).…”

Emerging covalent triazine framework-based nanomaterials for electrochemical energy storage and conversion

“…2e). [67][68][69][70] This methodology is straightforward, cheap, and more atomefficient in comparison to other pathways. The obtained CTFs also possess high thermo-chemical stability in a variety of aqueous and organic solvents.…”

The preparation of 3,4‐ethylenedioxy thiophene (EDOT)‐based conjugated microporous polymers by direct arylation polymerization and fluorescence‐sensing nitro‐aromatic compounds and iodine

“…6,12,13 Conventional C C coupling syntheses of thiophene-based CMPs have been put into effect by transition-metal catalyzed reactions, for instance, Sonogashira-Hagihara reactions, [8][9][10][14][15][16][17][18][19][20] Suzuki-Miyaura reactions, 18,[21][22][23] and Stille reactions. 11,24 Other coupling reactions are also widely used in the preparation of thiophene-based CMPs, for example, Schiff-base reversible condensation, [25][26][27][28] Friedel-Crafts arylation, 29,30 hypercrosslinked, 31,32 nucleophilic substitution, 33 trimerization of cyano 34,35 reactions. However, most of these reactions involve multiple steps of the functionalization of building blocks.…”