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Emergence of non-monotonic deep cavity cavitand assembly with increasing portal methylation

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Abstract

Octa-acid (OA) and tetra-endo-methyl octa-acid (TEMOA) are deep cavity cavitands that readily form multimeric complexes with hydrophobic guests, like n-alkanes, in aqueous solution. Experimentally, OA displays a monotonic progression from monomeric to dimeric complexes with n-alkanes of increasing length, while TEMOA exhibits a non-monotonic progression from monomeric, to dimeric, to monomeric, to dimeric complexes over the same range of guest sizes. Previously we have conducted simulations demonstrating this curious behavior arises from the methyl units ringing TEMOA's portal to its hydrophobic pocket barring the possibility for two alkane chains to simultaneously bridge between two hosts in a dimer. Here we expand our prior simulation study to consider the partially methylated hosts mono-endo-methyl octa-acid, 1,3-di-endo-methyl octa-acid, and tri-endo-methyl octa-acid to examine the emergence of non-monotonic assembly behavior. Our simulations demonstrate a systematic progression of non-monotonic assembly with increasing portal methylation. This behavior is traced to the progressive destabilization of 2 : 2 complexes (two hosts assembled with two guests) rather than stabilizing other potential host/guest complexes that could be formed.

Graphical abstract: Emergence of non-monotonic deep cavity cavitand assembly with increasing portal methylation

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Publication details

The article was received on 03 Jul 2019, accepted on 26 Sep 2019 and first published on 27 Sep 2019


Article type: Paper
DOI: 10.1039/C9ME00076C
Mol. Syst. Des. Eng., 2020, Advance Article
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    Emergence of non-monotonic deep cavity cavitand assembly with increasing portal methylation

    A. Saltzman, D. Tang, B. C. Gibb and H. S. Ashbaugh, Mol. Syst. Des. Eng., 2020, Advance Article , DOI: 10.1039/C9ME00076C

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