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A hemicryptophane cage bearing amine and amide functions in its three linkers was synthesized in five steps. The X-ray molecular structure of the cage shows a triple-stranded helical arrangement of the linkers stabilized by intramolecular hydrogen bonds between amide and amine groups. The chirality of the cyclotriveratrylene unit controls the propeller arrangement of the three aromatic rings in the opposite part of the cage. H NMR studies suggest that this structure is retained in solution.
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http://dx.doi.org/10.3762/bjoc.14.162 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, Diagonal 645, Barcelona, 08028, Spain.
Spins within molecules benefit from the atomistic control of synthetic chemistry for the realization of qubits. One advantage is that the quantum superpositions of the spin states encoding the qubit can be coherently manipulated using electromagnetic radiation. The main challenge is the fragility of these superpositions when qubits are to partake of solid-state devices.
View Article and Find Full Text PDFNat Commun
August 2025
Laboratory of Structural Cell Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, 50 South Dr., Bethesda, MD, 20892, USA.
SSNA1 is a fibrillar protein involved in dynamic microtubule remodeling, including nucleation, co-polymerization, and microtubule branching. The underlying molecular mechanism has remained unclear due to a lack of structural information. Here, we determine the cryo-EM structure of C.
View Article and Find Full Text PDFInorg Chem
August 2025
Central Hospital of Dalian University of Technology, School of Chemistry, Dalian University of Technology, Dalian 116024, China.
Rational design of chiral metallodrugs with precise stereochemical control and enhanced photodynamic performance is pivotal for advancing precision oncology. Herein, we report the stepwise assembly of homochiral dinuclear Ir(III) triple-stranded metallohelices (ΔΔ-/ΛΛ-) via dynamic imine ligation followed by reductive stabilization, yielding configurationally stable amine-bridged helical architectures with locked chirality. While both enantiomers exhibit comparable dark toxicities, the ΔΔ-enantiomer demonstrates enhanced photodynamic activity against multiple cancer cell lines under white light irradiation.
View Article and Find Full Text PDFChem Sci
August 2025
Department of Chemistry, Zhejiang University Hangzhou 310058 China.
A class of triple-stranded helicates based on six-coordinate silicon centres has been constructed through self-assembly of achiral catechol ligands, as confirmed by single-crystal X-ray diffraction. These architectures demonstrate stability across physiological environments at pH = 3-12. Ligand rigidity dictates chiral configurations: rigid scaffolds form ΛΛ/ΔΔ racemic helicates, while flexible linkers enable dynamic equilibration with ΛΔ mesostates, observable by NMR.
View Article and Find Full Text PDFInorg Chem
July 2025
Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai E. Ansermet, Geneva 4CH-1211, Switzerland.
The efficiency of intermetallic d-f energy transfers in molecular-based Fe(II)-Ln(III) dyads can be modulated by (i) the spin state of the [Fe(II)N] unit, (ii) the intermetallic distance, and (iii) the choice of the trivalent lanthanide (Ln(III)). The programming of a monotonous and reliable change in Ln-based luminescence upon spin-crossover (SCO) processes is highly desired for easy and fast optical monitoring of Fe(II)-spin state, but Ln···Fe separations over the nanometer range are required to be compatible with detectable Ln-based light emission. Moving from a nonluminescent rigid macrobicyclic dinuclear [FeEu()] triple-stranded helicate (Fe···Eu = 9.
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