For the past several years our group has been researching a novel class of nanoscale, self-assembling copper complexes capable of incarcerating a variety of multiply charged oxoanions, termed nanojars. In this poster, we present results of our investigation of the reactivity of carbonate-encapsulating nanojars with the formula {(CH3(CH2)3)4N}2[(Cu(OH)pz)nCO3], where n = 27, 29, 30, 31 and pz = pyrazolate, with a variety of weakly acidic compounds and their conjugate bases that can act as alternative ligands in the complex. These nanojars are known to be sensitive to even slightly acidic solutions despite exhibiting a strong resistance to decomposition in highly basic solutions (pH&gt;14). To investigate the characteristics of this acidic decomposition and the relative stability of the different sizes of the nanojars in solution, a microscale reaction scheme was developed to simulate a titration at a variety of molar equivalents of each acidic titrant (ranging from 1 to 200) analyzed by electrospray ionization mass spectrometric methods. General decomposition trends of the carbonate nanojars in acidic media, as well as substitution trends of the pyrazole or hydroxide species by the conjugate bases will be discussed. The reactions of carboxylic acids, dicarboxylic acids, tetrabutylammonium hydrogen carbonate and hydrogen sulfate salts, alcohols, thiols, and sulfonic acids will be examined. While it has been previously demonstrated that nanojars can tolerate a variety of substituents at different positions of the pyrazolate ligand, this is the first in depth investigation of the substitution of pyrazolate by other ligands. Our results show that in many cases a variety of ligands can substitute for pyrazolate or hydroxide, but that the tolerance of this is not always the same for all nanojar sizes.

Nanojar reactivity with acidic compounds and their conjugate base ligands

253rd National Meeting (2017)

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