Introduction of atropisomeric axes into a bent bispyridine ligand leads to the quantitative formation of a complex mixture of atropisomeric ML cages upon treatment with metal ions. Whereas the isomer ratio of the obtained cage mixture, consisting of up to 42 isomers, is insensitive to temperature and solvent, the quantitative convergence from the mixture to a single isomer is accomplished upon encapsulation of a large spherical guest, namely fullerene C. The observed isomerization with other guests depends largely on their size and shape (, <10 and 82% convergence with planar triphenylene and bowl-shaped corannulene guests, respectively). Besides the unusual guest-induced convergence, the present cage mixture displays the strongest guest emission ( = 68%) among previously reported M L cages and capsules, upon encapsulation of a BODIPY dye in water.
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http://dx.doi.org/10.1039/d0sc03223a | DOI Listing |
Angew Chem Int Ed Engl
December 2024
University of Barcelona: Universitat de Barcelona, Departament de Ciència dels Materials i Química Física, SPAIN.
The directional assembly of porous organic molecules into long-range ordered architectures, featuring controlled hierarchical porosity and oriented pore channels with defined spatial arrangements, is a fundamental challenge in chemistry and materials science. Herein, using porous organic cages as starting units, we present a cooperative multiscale-assembly strategy enabling the simultaneous alignment of pore channels and directional hierarchical growth in a single step. At the microscopic level, we employed double solvents to manipulate the intermolecular packing of microporous tetrahedral [4+6] imine cages (CC1 and CC3), resulting in pore channel orientation.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry and the UCR Center for Catalysis, University of California-Riverside, Riverside, California 92521, United States.
suite of internally functionalized FeL cage complexes has been synthesized with lipophilic end groups to allow dissolution in varied solvent mixtures, and the scope of their molecular recognition of a series of neutral, nonpolar guests has been analyzed. The lipophilic end groups confer cage solubility in solvents with a wide range of polarities, from hexafluoroisopropanol (HFIP) to tetrahydrofuran, and the hosts show micromolar affinities for neutral guests, despite having no flat panels enclosing the cavity. These hosts allow interrogation of the effects of an internal functional group on guest binding properties, as well as solvent-based driving forces for recognition.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Inorganic Chemistry, University of Granada and "Unidad de Excelencia en Química (UEQ)", Avda. Fuente Nueva s/n, Granada 18071, Spain.
The thermodynamically controlled self-assembly of bis-bidentate quaterpyridine ligand, L = 2,2':5',5″:2″,2‴-quaterpyridine, with Cr and subsequent oxidation to Cr yields the first photoluminescent tetrahedral [CrL] molecular cage. Single-crystal X-ray diffraction reveals the presence of two homochiral cages (ΛΛΛΛ and ΔΔΔΔ) in the unit cell that crystallize as a racemic mixture. Additionally, a PF anion is observed inside the cavity, in line with isostructural cages built with Ni or Fe.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Department of Chemistry and Chemical Biology, TU Dortmund University, Otto Hahn Str. 6, 44227 Dortmund, Germany.
A family of Pd cages prepared from ligands based on an axially chiral diamino-[1,1'-biazulene] motif (serving as a unique azulene-based surrogate of the ubiquitous BINOL moiety) is reported. We show that preparing a cage starting from the racemate of a shorter bis-monodentate ligand derivative, equipped with pyridine donor groups, leads to integrative ("social") chiral self-sorting, exclusively yielding the product, but only in a selection of solvents. This phenomenon is driven by individual solvent molecules acting as hydrogen bonding tethers between the amino groups of neighboring ligands, thereby locking the final coordination cage in a single isomeric form.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
School of Materials Science and Engineering, National Institute for Advanced Materials, TKL of Metal and Molecule-Based Material Chemistry Institution, Nankai University, Tianjin, 300350, P. R. China.
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