Metal-Assisted and Solvent-Mediated Synthesis of Two-Dimensional Triazine Structures on Gram Scale

Abstract

Covalent triazine frameworks are an emerging material class that have shown promising performance for a range of applications. In this work, we report on a metal-assisted and solvent-mediated reaction between calcium carbide and cyanuric chloride, as cheap and commercially available precursors, to synthesize two-dimensional triazine structures (2DTSs). The reaction between the solvent, dimethylformamide, and cyanuric chloride was promoted by calcium carbide and resulted in dimethylamino-s-triazine intermediates, which in turn undergo nucleophilic substitutions. This reaction was directed into two dimensions by calcium ions derived from calcium carbide and induced the formation of 2DTSs. The role of calcium ions to direct the two-dimensionality of the final structure was simulated using DFT and further proven by synthesizing molecular intermediates. The water content of the reaction medium was found to be a crucial factor that affected the structure of the products dramatically. While 2DTSs were obtained under anhydrous conditions, a mixture of graphitic material/2DTSs or only graphitic material (GM) was obtained in aqueous solutions. Due to the straightforward and gram-scale synthesis of 2DTSs, as well as their photothermal and photodynamic properties, they are promising materials for a wide range of future applications, including bacteria and virus incapacitation.

High-Crystallinity Covalent Organic Framework Synthesized in Deep Eutectic Solvent: Potentially Effective Adsorbents Alternative to Macroporous Resin for Flavonoids

“…From Figure C,D, it can be seen that COF-DES was crystalline, with a measured in-plane lattice constant of the hexagonal crystal of approximately 0.25 nm. These data corresponded well with the in-plane lattice constant of graphite ( a = 0.246 nm) …”

“…These data corresponded well with the in-plane lattice constant of graphite (a = 0.246 nm). 43 The functional groups on COF-DES were further confirmed by performing Fourier transform infrared (FT-IR) spectroscopy (Figure 3A). Compared with the FT-IR spectra of TPB and DHA, the N−H stretching band of TPB at 3208.4, 3341.6, and 3430.8 cm −1 (curve a of FT-IR), the CO stretching vibration band of DHA at 1667.6 cm −1 (curve b of FT-IR) weakened or disappeared in the FT-IR spectrum of COF-DES (curve c) as a result of the reaction.…”

Regulating Steric Hindrance in Redox‐Active Porous Organic Frameworks Achieves Enhanced Sodium Storage Performance

“…The ex situ X-ray photoelectron spectroscopy (XPS) technique was also employed (Figure 4b), and two major peaks located at 286.7 and 284.4 eV in C 1s spectrum can be assigned to the CN moiety of the triazine ring and CC unit of C6-benzene rings vibration, respectively. [19,28,29] After discharged to 0.01 V for the sodiation process, the peak intensity of CN slightly decreases, demonstrating the consumption of triazine rings. When charged back to 3.0 V, the CN peak can be restored, revealing a reversible reaction of triazine rings toward Na ions.…”

Graphitic Aza‐Fused π‐Conjugated Networks: Construction, Engineering, and Task‐Specific Applications

“…[73] It should be pointed out that herein, we will mainly focus on the approaches toward CTF construction starting from monomers with no triazine units being involved. Besides these, other methodologies using triazine units-containing monomers can also afford nanoporous CTFs with adjustable properties via monomer structure or reaction parameter controlling, which include but are not limited to cyanuric chloride with aromatic moieties via the Friedel-Crafts reaction catalyzed by Lewis acids (e.g., ZnCl 2 and AlCl 3 ) or superacids, [74][75][76][77] cyanuric chloride with electrophiles (amines, [78,79] calcium carbide, [80] or 1,3,5-triazine-2,4,6-trithiol [81] ), [82] melamine or 1,3,5-tris(4-aminophenyl) triazine with aromatic aldehydes catalyzed by organic acid, [83,84] aromatic triazine-containing aldehydes with amines via CC bond formation, [85] triazine-containing aromatic borate with aromatic bromides via Suzuki-Miyaura polycondensation, [33] triazine-containing carbazoles via oxidative coupling catalyzed by FeCl 3 , [86] and triazine-containing aromatic alkynes with triazine cores via homocoupling catalyzed by Cu species. [87] Some of the works have been well summarized in previous reviews related to CTFs.…”