112809-25-3Relevant articles and documents
An insight into the controllable synthesis of Cd(ii) complexes with a new multifunctional ligand and its application in dye-sensitized solar cells and luminescence properties
Gao, Song,Fan, Rui Qing,Wang, Xin Ming,Qiang, Liang Sheng,Wei, Li Guo,Wang, Ping,Zhang, Hui Jie,Yang, Yu Lin,Wang, Yu Lei
, p. 6053 - 6063 (2015)
Based on a new design of 4-cyanobenzyl-based 1,2,4-triazole ligand 4-(1,2,4-triazolylmethyl) cyanobenzene (TMCB), a series of cadmium complexes 1-5′ from a mononuclear to three-dimensional (3D) structure have been synthesized through hydro(solvo)thermal reactions; they were generally formulated as [Cd(TMCBA)2]n (1), [Cd(TMCB)(1,4-bda)(H2O)]n (2), {[Cd2(TMCB)4(1,4-bda)2(H2O)2]n·3H2O}n (3), {[Cd(TMCB)4(H2O)2]·(NO3)2·(H2O)2}n (4), [Cd1.5(1,4-bda)1.5(DMF)2]2n (5) and [Cd1.5(1,4-bda)1.5(DMF)2]2n (5′) (TMCBA = 4-(1,2,4-triazolylmethyl) benzoic acid, which is formed from the hydrolysis of TMCB; 1,4-H2bda = 1,4-benzenedicarboxylic acid; the difference between two genuine supramolecular isomers of 5 and 5′ is the use of TMCB as the additive agent for the reaction). Complexes 1-5′ exhibit tunable luminescence with emission maxima containing deep blue, blue, light blue, green and deep green region at 298 K or 77 K in both different solvents (polarity: DMSO > CH3OH > CHCl3) and solid state. Interestingly, the good thermal stability accompanied by their compensated adsorption to ruthenium complex N719 in the region of low wavelength, enabled 1 and 4 to serve as co-sensitizers in combination with N719 in dye sensitized solar cells (DSSCs). After co-sensitization with N719, the overall conversion efficiency of 1 and 4 were found to be 7.68% and 6.85%, which are 40.40% and 25.23% higher than that for DSSCs only sensitized by N719 (5.47%) under the same conditions, respectively. The improvement in efficiency is attributed to the fact that complexes 1 and 4 overcome the deficiency of N719 absorption in the low wavelength region of ultraviolet and blue-violet, offset competitive visible light absorption of I3- and reduce charge recombination due to the formation of an effective cover layer of the dye molecules on the TiO2 surface. As a result, the synthesized complexes are promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.
Taming Ambident Triazole Anions: Regioselective Ion Pairing Catalyzes Direct N-Alkylation with Atypical Regioselectivity
Dale, Harvey J.A.,Hodges, George R.,Lloyd-Jones, Guy C.
, p. 7181 - 7193 (2019/05/10)
Controlling the regioselectivity of ambident nucleophiles toward alkylating agents is a fundamental problem in heterocyclic chemistry. Unsubstituted triazoles are particularly challenging, often requiring inefficient stepwise protection-deprotection strategies and prefunctionalization protocols. Herein we report on the alkylation of archetypal ambident 1,2,4-triazole, 1,2,3-triazole, and their anions, analyzed by in situ 1H/19F NMR, kinetic modeling, diffusion-ordered NMR spectroscopy, X-ray crystallography, highly correlated coupled-cluster computations [CCSD(T)-F12, DF-LCCSD(T)-F12, DLPNO-CCSD(T)], and Marcus theory. The resulting mechanistic insights allow design of an organocatalytic methodology for ambident control in the direct N-alkylation of unsubstituted triazole anions. Amidinium and guanidinium receptors are shown to act as strongly coordinating phase-transfer organocatalysts, shuttling triazolate anions into solution. The intimate ion pairs formed in solution retain the reactivity of liberated triazole anions but, by virtue of highly regioselective ion pairing, exhibit alkylation selectivities that are completely inverted (1,2,4-triazole) or substantially enhanced (1,2,3-triazole) compared to the parent anions. The methodology allows direct access to 4-alkyl-1,2,4-triazoles (rr up to 94:6) and 1-alkyl-1,2,3-triazoles (rr up to 99:1) in one step. Regioselective ion pairing acts in effect as a noncovalent in situ protection mechanism, a concept that may have broader application in the control of ambident systems.
A base-induced ring-opening process of 2-substituted-1,3,4-oxadiazoles for the generation of nitriles at room temperature
Lu, Guo-Ping,Lin, Ya-Mei
, p. 371 - 374 (2014/07/08)
A novel base-catalysed 1,3,4-oxadiazole fragmentation for the synthesis of nitriles at room temperature has been developed. This reaction is performed under transition-metal-free conditions, and provides a new ring cleavage reaction of 1,3,4-oxadiazoles in organic synthesis.
