Molecular tectonics: tetracarboxythiacalix[4]arene derivatives as tectons for the formation of hydrogen-bonded networks

A S Ovsyannikov,S Ferlay,N Kyritsakas,A I Konovalov,M N Lang,M W Hosseini,I S Antipin,S E Solovieva

doi:10.1039/c6ce02026g

Abstract

A series of thiacalix[4]arene derivatives blocked in the 1,3-alternate conformation and bearing four carboxylic acids have been designed and synthesized. These compounds, owing to the H-bond donor (OH moiety) and acceptor (CO group) nature of the carboxylic acid moieties, behave as self-complementary tectons and lead to the formation of tubular 1D H-bonded networks in the crystalline phase. Upon deprotonation of the self-complementary neutral compounds, i.e. transformation of carboxylic acid moieties into carboxylates, anionic tectons are generated. Due to their propensity to form H-bonded networks in the presence of a dicationic H-bond donor tecton of the cyclic bis-amidinium type, designed to behave as a molecular staple interconnecting two carboxylates moieties, 1- and 2-D H-bonded networks are formed under self-assembly conditions.

Highlights

Tubular architectures1–3 are of interest as they form channels that may lead to the transport of neutral or charged species
We describe their selfassembly in the crystalline phase into 1D tubular H-bonded networks as well as combinations of their deprotonated derivatives as anionic tectons with a dicationic tecton A2+, behaving as a molecular staple, capable of bridging consecutive anionic units, leading to extended H-bonded networks
Compounds 4–8 bearing four carboxylic acid moieties were obtained in 46–95% yield upon hydrolysis of the tetraester derivatives 4′–8′

Summary

Introduction

Tubular architectures1–3 are of interest as they form channels that may lead to the transport of neutral or charged species. Compounds 4–8 bearing four carboxylic acid moieties were obtained in 46–95% yield upon hydrolysis of the tetraester derivatives 4′–8′ (see ESI,† Table S1). Formation of extended 1D tubular architectures by selfcomplementary tectons 4–8 Owing to the propensity of carboxylic acids to form a H-bonded dimeric complex (Fig. 2b) and due to the 1,3-A conformation adopted by the tetracarboxyl compounds 4–8, the latter might behave as self-complementary tectons and self-assemble into 1D H-bonded tubular networks (Fig. 2a).

Results

Conclusion