P,N-Containing cyclophanes with large helical hydrophobic cavities: prospective precursors for the design of a molecular reactor

Abstract

The highly effective self-assembly process between 2,4,6-tris(isopropyl)phenylphosphine or mesitylphosphine, formaldehyde and 1,4-bis(alpha-(4'-aminophenyl)isopropyl)benzene results in the formation of a novel type of heterocyclophane which is able to encapsulate organic molecules as well as being a potential ligand for transition metals inside the intramolecular cavity. Compounds of this type can be regarded as potential precursors for a new kind of molecular reactors.

Structure, Conformation, and Dynamics of P,N-Containing Cyclophanes in Solution

“…One of them (A) is "cylindrical" and highest in energy. The other two forms (B and C) are helical with different twisting: B is similar to the structure of 1 found in the solid state 29 while C is more twisted (Figure 4, as a measure of torsion the angles between the phosphorus-phosphorus axes are used).…”

Cyclic aminomethylphosphines as ligands: Balancing between rational design and unpredicted findings

“…10 Unexpectedly an effective strategy of P,N-containing macrocycles design was developed based on covalent self-assembly processes in the course of Mannich-type condensations in threecomponent systems: primary phosphine (or secondary diphosphine) --formaldehyde --diamine with spatially divided functional groups (or primary amine). 11 This approach (Scheme 2) allowed to obtaine various types of macrocyclic phosphines, namely cage cyclophanes with 1,5-diaza-3,7-diphosphacyclooctane fragment in the basic framework, [12][13][14][15] cyclophanes with linear P,Ncontaining spacers, 11 P,N-containing corands 11, 16-18 and the first P,N-containing cryptand 19,20 with four phosphine centers. 5 However novel ligands showed unpredicted properties like unique reversible slitting of macrocycles on to the smaller cycles, 18 rapid interconversion of isomers catalyzed by both acids and transitional metals, 21 bridging behavior of usually chelating ligands and an unexpectedly high influence of dangling substituents on N-atoms on to the catalytic and luminescent properties of P-complexes.…”

A Pt(II)‐based Hexagonal Ionic Supramolecular Coordination Complex and its DNA Interactions.

“…Often, design of these complex abiological supramolecular frameworks (SCCs) are inspired by nature and these have practical applications such as their use as molecular sensors, catalytic systems mimicking enzymes or molecular reactors to yield unusual products. An equally exciting and emerging research interest is to explore the nature of interaction of SCCs and biological entities such as nucleic acids (DNA or RNA), proteins, and cells (normal and cancerous) .…”