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

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.

Synthesis of a Black Dye with Absorption Capabilities Across the Visible-to-Near-Infrared Region: A MO-Mixing Approach via Heterometal Coordination of Expanded Porphyrinoid.

An expanded metalloporphyrin-based "black dye" Au-Pd oxohexaphyrin (AuPd-1) with absorption capabilities across the visible-to-near-infrared (NIR) range was synthesized. This black dye, AuPd-1, possessed efficient light-harvesting and photostable capabilities, which were indicative of superior photothermal (PT) conversion abilities. Encapsulation of AuPd-1 with a micellar nanocapsule resulted in a compound that demonstrated intense photoacoustic (PA) properties in the NIR region in water. This finding indicated how metal (d)-ligand (π) molecular orbital interactions in metalloporphyrins could aid in the design of visible-to-NIR light-harvesting black dyes for PT and PA applications.