The handedness of a supramolecular chiral aggregate is often assigned based on the sign of circular dichroism spectra, adopting the exciton chirality method. However, the method does not properly account for the nature of intermolecular interactions. We introduce a generalized picture on the use of the sign of chiral signals in determining the helicity of chiral aggregates, rooted in the exciton model, supported by TD-DFT results.
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http://dx.doi.org/10.1039/d0cc01922d | DOI Listing |
Spectrochim Acta A Mol Biomol Spectrosc
January 2025
State Key Laboratory of Green Pesticide, Central China Normal University, Wuhan 430079, PR China. Electronic address:
The construction of helical structures through self-assembly and the exploration of their formation mechanisms not only amplify chiroptical properties but also provide profound insights into the structures and functions of natural helices. In this study, we developed a chiral Au(I) system based on BINAP and alkynyl ligands. The modification of the length or number of alkyl chains at the terminal positions of the alkynyl ligands significantly impacted the self-assembly behavior of the complexes.
View Article and Find Full Text PDFChemistry
January 2025
Natinal Institute of Adavanced Industrial Science and Technology, Interdisciplinary Research Center for Catalytic Chemistry, Higashi 1-1-1, 305-8565, Tsukuba, JAPAN.
Unprecedented (2E,4E,6Z,8Z)-nona-2,4,6,8-tetraenoate derivatives highly substituted by aryl groups have been synthesized by the reaction of rhodium complexes having aryl-substituted hexa-1,3,5-trienyl ligands with acrylates. These compounds have potential axial chirality, and their enantiomers are isolable by the chiral HPLC technique. Although the racemization barrier of isolated enantiomers was not high, it was found that a cyclic dimer synthesized by head-to-tail transesterification of a modified analog has quite a stable axial chirality even at a high temperature.
View Article and Find Full Text PDFMaterials (Basel)
January 2025
College of Chemistry, Sichuan University, Chengdu 610064, China.
Circularly polarized luminescence (CPL) is an emerging field with significant applications in molecular electronics, optical materials, and chiroptical sensing. Achieving efficient CPL emission in organic systems remains a major challenge, particularly in the development of materials with high fluorescence quantum yields (Φ) and large luminescence dissymmetry factors (g). Herein, we report the efficient synthesis of shape-persistent tetraphenylethylene macrocycles and investigate its potential as a CPL material.
View Article and Find Full Text PDFACS Appl Bio Mater
January 2025
School of Chemistry, Pharmacy and Food Biosciences, University of Reading, Whiteknights, Reading RG6 6AD, U.K.
A series of tripodal (three-arm) lysine-based peptides were designed and synthesized and their self-assembly properties in aqueous solution and antimicrobial activity were investigated. We compare the behaviors of homochiral tripodal peptides (KKY)K and a homologue containing the bulky aromatic fluorenylmethoxycarbonyl (Fmoc) group Fmoc-(KKY)K, and heterochiral analogues containing k (d-Lys), (kkY)K and Fmoc-(kkY)K. The molecular conformation and self-assembly in aqueous solutions were probed using various spectroscopic techniques, along with small-angle X-ray scattering (SAXS) and cryogenic-transmission electron microscopy (cryo-TEM).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute of Organic Chemistry, University Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany.
In ion-pair catalysis, the last intermediate structures prior to the stereoselective transition states are of special importance for predictive models due to the high isomerization barrier between - and -substrate double bonds connecting ground and transition state energies. However, in prior experimental investigations of chiral phosphoric acids (CPA) solely the early intermediates could be investigated while the key intermediate remained elusive. In this study, the first experimental structural and conformational insights into ternary complexes with CPAs are presented using a special combination of low temperature and relaxation optimized N HSQC-NOESY NMR spectroscopy to enhance sensitivity.
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