Understanding the fundamentals and applications of chirality relies substantially on the amplification of chirality through hierarchical assemblies involving various weak interactions. However, a notable challenge remains for metal clusters chiral assembly driven by halogen bonding, despite their promising applications in lighting, catalysis, and biomedicine. Here, we used halogen bonding-driven assembly to achieve a hierarchical degree of achiral emissive clusters. From single crystals to one-dimensional ribbons and then to helixes, the morphologies were primarily modulated by intermolecular halogen bonding that evoked by achiral or/and chiral iodofluorobenzene (IFBs) molecules. Concomitantly, the luminescence and circularly polarized luminescence (CPL) changed a lot, ultimately leading to a substantial increase in the luminescence dissymmetry -factor () of 0.036 in the supramolecular helix. This work opens an avenue for hierarchical assemblies using predesigned metal clusters as building blocks though directional halogen bonding. This achievement marks a noteworthy advancement in the field of nanosized inorganic functional blocks.
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http://dx.doi.org/10.1126/sciadv.adj9013 | DOI Listing |
Inorg Chem
December 2024
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai 980-8578, Japan.
One of the goals in synthetic chemistry is to obtain compounds featuring unusual valence states that are stable under ambient conditions. At present, stabilizing unusual Pt(III) states is considered difficult, except through direct Pt-Pt bonding such as that in platinum-blues or organometallization using bulky ligands. Pt(III) stabilization is also very difficult in halogen-bridged metal complex chains (MX-Chains).
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Oklahoma State University, 107 Physical Sciences, Stillwater, Oklahoma 74078, United States.
While charge-transfer complexes involving halogen-bonding interactions have emerged as an alternative strategy for the photogeneration of carbon radicals, examples using (fluoro)alkyl bromides are limited. This report describes a dual catalytic approach for radical generation from α-bromodifluoroesters and amides under visible-light irradiation. Mechanistic studies suggest that the reaction proceeds through bromide displacement using a catalytic iodide salt, generating a C-I bond that can be engaged by our halogen-bonding photocatalysis platform.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
School of Applied and Interdisciplinary Sciences, Indian Association for the Cultivation of Science (IACS), 2A and 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700032, India.
This study explores peptide-mediated chiral induction and circularly polarized luminescence (CPL) in achiral BODIPY dyes, leading to a high value of up to -1.2 × 10 through orthogonal halogen bonding and hydrogen bonding. It unravels the impact of these combined directional interactions on the formation of heterostructures and their thermal stability.
View Article and Find Full Text PDFACS Med Chem Lett
December 2024
Department of Pharmaceutical Chemistry, Faculty of Pharmacy, University of Ljubljana, Aškerčeva cesta 7, 1000 Ljubljana, Slovenia.
In this Letter, we present a small series of novel bacterial topoisomerase inhibitors (NTBIs) that exhibit both potent inhibition of DNA gyrase and potent antimycobacterial activity. The disclosed crystal structure of DNA gyrase in complex with DNA and compound from this NBTI series reveals the binding mode of an NBTI in the GyrA binding pocket and confirms the presence and importance of halogen bonding for the excellent on-target potency. In addition, we have shown that compound is a promising DNA gyrase inhibitor, with an IC for gyrase of 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
Halogen-bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor-acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge-balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration.
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