Cyclotriveratrylene and Cryptophanes

Abstract

A review of the chemistry and applications of cyclotriveratrylenes (CTVs) and cryptophanes is given. Synthetic approaches to CTVs and cryptophanes are discussed, including the recently reported mild cyclization conditions and strategies for the synthesis of lower symmetry cryptophanes. Host– guest and inclusion chemistry is surveyed, including binding of neutral and organic cations by cryptophanes in solution, clathrate structures of CTVs, the anion‐binding abilities of metalled CTVs and cryptophanes, the fullerene‐binding abilities of CTVs, and xenon binding by cryptophanes and their potential applications in xenon biosensors for imaging applications. The uses of CTVs and crytophanes as molecular platforms for other supramolecular chemistry applications are also discussed. These include development of coordination polymers with CTVs and cryptophanes; organic and metallo‐supramolecular prism‐like assemblies, some of which show unusual molecular topologies; and self‐organized systems such as liquid crystals and gels.

Supramolecular Polymer Networks: Preparation, Properties, and Potential

“…Several classes of macrocycles have been developed, including crown ethers [199,200], porphyrins [201,202], cyclophanes [203], catenanes [204], cavitands [205,206], cryptophanes [207], calix[n]arenes [208], and carcerands [209]. Macrocyclic-based supramolecular gels can either be formed from low molecular weight precursors or from macromolecular building blocks.…”

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

“…Cyclotriveratrylene (CTV, 1 ), a [1.1.1]orthocyclophane, is an archetypal cyclophane scaffold that is commonly employed in supramolecular chemistry. − As part of our research program directed toward the synthesis and application of apex-modified CTV derivatives − with unique material properties and applications involving host–guest chemistry, we recently reported the synthesis of the new triazaorthocyclophane 2a (Figure ) which was alkylated to give the N , N ′, N ″-trimethyl derivative 2b . Following a six-step linear sequence to obtain the precursor 3a (Scheme ), two mechanistically different approaches were examined in order to obtain the final desired triazacyclophane 2a (Scheme ).…”

Self-Assembly and Host–Guest Interactions of Pd3L2 Metallo-cryptophanes with Photoisomerizable Ligands

“…Our research focuses on metallo-supramolecular chemistry of the cyclotriveratrylene (CTV) family of host molecules. CTV-type host molecules feature a tribenzo­[ a,d,g ]­cyclononene scaffold with a bowl conformation, an open upper rim, and a hydrophobic binding cavity . Tripodal analogues of CTV with ligand groups appended to the upper rim of the bowl are chiral and have proved to be ideal for the self-assembly of metallo-cages, as they have an orthogonal arrangement of metal-binding groups and a deep cavity .…”