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      Temperature Controls Guest Uptake and Release from Zn 4L 4 Tetrahedra

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          Abstract

          We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations ( T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host–guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.

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          Most cited references18

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          Supramolecular transformations within discrete coordination-driven supramolecular architectures.

          In this review, a comprehensive summary of supramolecular transformations within discrete coordination-driven supramolecular architectures, including helices, metallacycles, metallacages, etc., is presented. Recent investigations have demonstrated that coordination-driven self-assembled architectures provide an ideal platform to study supramolecular transformations mainly due to the relatively rigid yet dynamic nature of the coordination bonds. Various stimuli have been extensively employed to trigger the transformation processes of metallosupramolecular architectures, such as solvents, concentration, anions, guests, change in component fractions or chemical compositions, light, and post-modification reactions, which allowed for the formation of new structures with specific properties and functions. Thus, it is believed that supramolecular transformations could serve as another highly efficient approach for generating diverse metallosupramolecular architectures. Classified by the aforementioned various stimuli used to induce the interconversion processes, the emphasis in this review will be on the transformation conditions, structural changes, mechanisms, and the output of specific properties and functions upon induction of structural transformations.
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            Functional Capsules via Subcomponent Self-Assembly

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              Fluorescent Flippers for Mechanosensitive Membrane Probes

              In this report, “fluorescent flippers” are introduced to create planarizable push–pull probes with the mechanosensitivity and fluorescence lifetime needed for practical use in biology. Twisted push–pull scaffolds with large and bright dithienothiophenes and their S,S-dioxides as the first “fluorescent flippers” are shown to report on the lateral organization of lipid bilayers with quantum yields above 80% and lifetimes above 4 ns. Their planarization in liquid-ordered (Lo) and solid-ordered (So) membranes results in red shifts in excitation of up to +80 nm that can be transcribed into red shifts in emission of up to +140 nm by Förster resonance energy transfer (FRET). These unique properties are compatible with multidomain imaging in giant unilamellar vesicles (GUVs) and cells by confocal laser scanning or fluorescence lifetime imaging microscopy. Controls indicate that strong push–pull macrodipoles are important, operational probes do not relocate in response to lateral membrane reorganization, and two flippers are indeed needed to “really swim,” i.e., achieve high mechanosensitivity.
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                Author and article information

                Journal
                J Am Chem Soc
                J. Am. Chem. Soc
                ja
                jacsat
                Journal of the American Chemical Society
                American Chemical Society
                0002-7863
                1520-5126
                03 September 2019
                18 September 2019
                : 141
                : 37
                : 14534-14538
                Affiliations
                []Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, United Kingdom
                []Department of Chemistry, Randolph-Macon College , Ashland, Virginia 23005, United States
                Author notes
                Article
                10.1021/jacs.9b07307
                6753657
                31478658
                3843cd4c-916e-41e5-b730-2157e611cf96
                Copyright © 2019 American Chemical Society

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

                History
                : 10 July 2019
                Categories
                Communication
                Custom metadata
                ja9b07307
                ja-2019-07307p

                Chemistry
                Chemistry

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