Three host peculiarities of a cycloalkane-based micelle toward large metal-complex guests

Abstract

Linear alkanes are essential building blocks for natural and artificial assemblies in water. As compared with typical, linear alkane-based micelles and recent aromatic micelles, we herein develop a cycloalkane-based micelle, consisting of bent amphiphiles with two cyclohexyl frameworks. This uncommon type of micelle, with a spherical core diameter of ~ 2 nm, forms in water in a spontaneous and quantitative manner. The cycloalkane-based, hydrophobic cavity displays peculiar host abilities as follows: (i) highly efficient uptake of sterically demanding Zn(II)-tetraphenylporphyrin and rubrene dyes, (ii) selective uptake of substituted Cu(II)-phthalocyanines and spherical nanocarbons, and (iii) uptake-induced solution-state emission of [Au(I)-dimethylpyrazolate]3 in water. These host functions toward the large metal-complex and other guests studied herein remain unaccomplished by previously reported micelles and supramolecular containers.

Chiral Water-Soluble Molecular Capsules With Amphiphilic Interiors

“…To mimic this compartmentalization concept, chemists aim at the creation of artificial molecular container molecules (capsules and cages) that operate under various conditions. For obtaining water-soluble and water-stable capsules, numerous covalent and noncovalent strategies have been tested, involving self-assembly by coordination bonds ( Yi et al, 2012 ; Yamashina et al, 2014 ; Cullen et al, 2015 ; Taylor et al, 2019 ; Percástegui et al, 2020 ), electrostatic interactions ( Corbellini et al, 2005 ; Martin et al, 2011 ; Zadmard et al, 2013 ), or hydrophobic clustering ( Gibb and Gibb, 2004 ; Hiraoka et al, 2010 ; Kondo et al, 2013 ; Suzuki et al, 2013 ; Jordan and Gibb, 2015 ; Suzuki et al, 2016 ; Kondo et al, 2017 ; Zhan et al, 2018 ; Hanafusa et al, 2020 ; Ashbaugh et al, 2021 ). Additional stabilization coming from interactions with guests (templation approach) is often beneficial or even crucial for stability ( Zhang et al, 2013 ; Ayhan et al, 2015 ; Tiefenbacher et al, 2015 ; Rahman et al, 2020 ), which, however, blocks the cavity for further applications.…”

Supramolecular Singlet Fission of Pentacene Dimers within Polyaromatic Capsules

“…The tuning of the SF characters of not only the covalent dimer but also the noncovalent one was demonstrated for the first time using our capsules. On the basis of the present investigation, we emphasize the future importance of the supramolecular host–guest strategy, namely, the use of multiple noncovalent interactions in confined nanospaces, − ,,− to generate, enhance, or tune the singlet fission of new as well as previously studied pentacene derivatives.…”

Self-Assembled Nanodot Actuator with Changeable Fluorescence by π–π Stacking Force Based on a Four-Armed Foldable Phthalocyanine Molecule and Its Supersensitive Molecular Recognition

“…Pcs are emerging as ideal building blocks for supramolecular assembly of nanodots for intelligent nanodevices, molecular recognition, and photodynamic therapy. However, most of the fluorescent sensors are “on–off” switch mode with a single signal, in which the fluorescence of the host molecule quenches or becomes weaker during the guest molecule recognition. − Designing novel smart fluorescence switches and actuators based on the “off–on” mode which have high sensitivity and intelligent response is, therefore, more desirable for scientific applications. − During the recognition process, the fluorescence of the host molecule becomes stronger when it recognizes the guest molecule.…”