A comprehensive reactivity study of nanojars toward different acidic compounds with varying pKa, including carboxylic acids (both aliphatic and aromatic mono- and dicarboxylic acids), substituted pyrazoles, p-toluenesulfonic acid, hydrogen sulfate, hydrogen carbonate, carbonic acid, 1-decanethiol, methanol, as well as different conjugate bases (formate, acetate, benzoate, 2-bromoethanesulfonate) was carried out with the aid of electrospray-ionization mass spectrometry. Thus, the effect on nanojar substitution and breakdown pattern of a number of variables, such as concentration of reagent (acid or conjugate base), acidity of reagent (pKa), effect of acid vs. conjugate base, steric effects, aromaticity, incarcerated anion and size of the nanojar, is evaluated. Of the substitution and breakdown products identified by mass spectrometry, acetate-substituted nanojars (Bu4N)2[CO3{Cu27(μ-OH)27(μ-pz)27−x(μ-CH3COO)x}] (x = 1 and 2), as well as dimeric complexes (Bu4N)2[Cu2(μ-pz)2A2] (A = CO32− and SO42−) have been isolated and characterized by single-crystal X-ray diffraction. This study offers a detailed understanding of the behavior of nanojars of various sizes and with different incarcerated anions in the presence of the above-mentioned compounds at varying concentrations and tests the limits of the pyrazolate/carboxylate structural analogy in multinuclear metal complexes. The results indicate that nanojar derivatives can be obtained by post-synthetic functionalization via pyrazolate/carboxylate or pyrazolate/pyrazolate ligand exchange.

Postsynthetic nanojar functionalization by pyrazolate/carboxylate and pyrazolate/pyrazolate ligand exchange

256th National Meeting (2018)

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