Amphiphilic Perylene–Calix[4]arene Hybrids: Synthesis and Tunable Self-Assembly

Abstract

The first highly water-soluble perylene-calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π-π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficient water solubility at slightly basic conditions. The tetrahedrally shaped amphiphile displays an unprecedented aggregation behavior down to concentrations as low as 10(-7) mol L(-1). The intriguing self-assembly process of the compound in water as well as under changed polarity conditions, achieved by addition of THF, could be monitored by the complemented use of cryogenic transmission electron microscopy (cryo-TEM), UV-vis spectroscopy, and fluorescence spectroscopy. Molecular-dynamics and molecular modeling simulations helped in understanding the interplay of supramolecular and optical behavior.

Supramolecular Catalysts Based on Novel Pyrimidinophane: Influence of Additives of Polymer and Lanthanum Ions

“…[14][15] Заслуживающей внимания стратегией модификации макроциклических соединений является введение в структуру различных функциональных групп и алкильных радикалов различной протяженности. [16][17][18] Это наделяет систему способностью к самоорганизации, [19][20] что позволяет качественно усовершенствовать функциональную активность систем. В частности, показана возможность использования функционали-зированной каликсареновой платформы для эффективного связывания и транспорта ДНК.…”

Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials

“…(d) Perspective (left) and top view (right) of a proposed cylindrical micelle arrangement of the closed conformers of the fibrous aggregates that are observed in the binary water/THF mixtures. Dimensions of the model correspond to the observed fibrous aggregates.The open space in the core volume of the cylindrical micelle is thought to be filled with THF 256. …”

A Competing Hydrogen Bonding Pattern to Yield a Thermo‐Thickening Supramolecular Polymer

“…Ester-bis-ureas contain both as trong bis-urea sticker that is responsible for the build-up of long rod-like objects by hydrogen bonding and ester groups that can interfere with this main pattern in as ubtle way. [14] An umber of studies describe the possibility of selecting one of these nanostructures by carefully controlling the conditions of aggregation, namely,t ime, [15][16][17][18] concentration, [19] temperature, [20] solvent, [21][22][23][24][25] and diffusion, [26] or by tuning the nature of the monomer. The transition from the low-temperature structure to the next occurs reversibly by heating and is accompanied by an increase in viscosity,arare feature for solutions in hydrocarbons.…”

“…[1][2][3][4] Ther eversible but directional non-covalent interactions responsible for their self-assembly provides tunability and responsiveness [5] to various stimuli. [14] An umber of studies describe the possibility of selecting one of these nanostructures by carefully controlling the conditions of aggregation, namely,t ime, [15][16][17][18] concentration, [19] temperature, [20] solvent, [21][22][23][24][25] and diffusion, [26] or by tuning the nature of the monomer. [14] An umber of studies describe the possibility of selecting one of these nanostructures by carefully controlling the conditions of aggregation, namely,t ime, [15][16][17][18] concentration, [19] temperature, [20] solvent, [21][22][23][24][25] and diffusion, [26] or by tuning the nature of the monomer.…”

“…This has contributed to the development of innovative catalysts, [6,7] fluorescent systems, [8,9] self-healing materials, [10,11] and gels, [12,13] among other potential applications.O ne fascinating consequence of the dynamic character of supramolecular assemblies is the capability of molecular building blocks to assemble into distinct thermodynamically or kinetically stable nanostructures. [14] An umber of studies describe the possibility of selecting one of these nanostructures by carefully controlling the conditions of aggregation, namely,t ime, [15][16][17][18] concentration, [19] temperature, [20] solvent, [21][22][23][24][25] and diffusion, [26] or by tuning the nature of the monomer. [27][28][29] This pathway complexity in the aggregation ability of the monomers is usually revealed by spectroscopic techniques that identify the structural differences in the assemblies at the nano or mesoscale (for example,kinetics of aggregation, helicity,s tacking mode,c onformation).…”