Abstract

The formation and decomposition of inclusion compounds with a solid-solid phase transition may be very selective to the guest molecular structure. This selectivity may function in essentially different ways than defined by the classical concept of molecular recognition, which implies the preferential binding of complementary molecules. Solid inclusion compounds may take part as an initial or/and final state in several processes of different types summarized in this review, which selectivity is boosted by cooperativity of participating molecular crystals. Some of these processes resemble switching electronic devices and can be called smart giving practically absolute molecular recognition.

Highlights

  • Molecular recognition of neutral molecules is one of the key problems in chemical technologies and in analytical and biotechnological applications (Reinhoudt, 2013; Persch et al, 2015; Shu et al, 2018)

  • This review describes the possible alternatives to the classical key-to-lock principle with a higher selectivity of molecular recognition

  • If the host has a permanent porosity combined with flexible structure, like that of some metal organic frameworks (MOFs) (Hiraide et al, 2016; Engel et al, 2017) or silicalites (DeJaco et al, 2019), the initial part of sorption isotherm may have the shape of Langmuir isotherm followed by a sigmoidal step

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Summary

INTRODUCTION

Molecular recognition of neutral molecules is one of the key problems in chemical technologies and in analytical and biotechnological applications (Reinhoudt, 2013; Persch et al, 2015; Shu et al, 2018). To reach a sufficient selectivity, host compounds with very complex structure are synthesized (Ariga et al, 2012; Zhang et al, 2019) to fit the well-known key-to-lock concept of molecular recognition formulated by Fischer (1894) This concept later developed in supramolecular chemistry is based on complementarity of two interacting molecules, where the host interacts with guest cooperatively through several more or less strong coordinate, donor-acceptor, and hydrogen bonds having a specific spatial arrangement (Joyce et al, 2010; Sonnenberg et al, 2012). The guest is not included, and below and above this threshold the composition of the solid phase does not change

Smart Molecular Recognition
CRYSTALLIZATION SELECTIVITY OF AMORPHOUS HOST
SELECTIVITY BY CAPACITY AND GIBBS ENERGY OF GUEST INCLUSION
SELECTIVITY OF INCLUSION IRREVERSIBILITY
SELECTIVITY OF GUEST EXCHANGE IN INCLUSION COMPOUND
SELECTIVITY BY A NUMBER OF STEPS OF GUEST INCLUSION AND RELEASE
CONCLUSIONS
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