Aggregation-induced emission (AIE)-based circularly polarized luminescence (CPL) has been recognized as a promising pathway for developing chiroptical materials with high luminescence dissymmetry factors (||). Here, we propose a method for the construction of a thermally tunable CPL-active system based on a supramolecular self-assembly approach that utilizes helical nano- or microfilament templates in conjunction with an AIE dye. The CPL properties of the ensuing ensembles are predominantly determined by the intrinsic geometric differences among the various filament templates such as their overall dimensions (width, height, and helical pitch) and the area fraction of the exposed aromatic segments or sublayers. The proposed mechanism is based on the collective data acquired by absorption, steady state and time-resolved fluorescence, absolute quantum yield, and CPL measurements. The highest || value for the most promising dual-modulated helical nanofilament templates in the present series was further enhanced, reaching up to || = 0.25 by confinement in the appropriate diameter of anodized aluminum oxide (AAO) nanochannels. It is envisioned that this methodology will afford new insights into the design of temperature-rate indicators or anti-counterfeiting tags using a combination of structural color by the nano- and microfilament templates and the AIE property of the guest dye.
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http://dx.doi.org/10.1021/acsami.2c05012 | DOI Listing |
Chirality
January 2025
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Narashino, Japan.
The synthesis, structure, and circularly polarized luminescence (CPL) properties of axially chiral boron difluoride complexes are described. A series of optically pure bis (boron difluoride) complexes were prepared in 5 steps from commercially available (S)- or (R)-BINOL as starting materials. The complexes were found to exhibit similar yellow photoluminescence in solution, regardless of the type of substituents on the nitrogen atoms.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
College of Mechanics and Engineering Science, Hohai University, Nanjing, 211100, China.
Driven by the pressing demand for integration and miniaturization within the terahertz (THz) spectrum, this research introduces an innovative approach to construct chiral structures using dichroism as the target function. This initiative aims to tackle the prevalent issues of single-functionality, narrow application scope, and intricate design in conventional metasurfaces. The proposed multifunctional tunable metasurface employs a graphene-metal hybrid structure to address the critical constraints found in existing designs.
View Article and Find Full Text PDFSpectrochim 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 PDFChemistry
January 2025
Beijing Normal University, College of Chemistry, Xiejiekou NO.19, 100875, Beijing, CHINA.
Optically pure monosubstituted [n]paracyclophanes are promising candidates for material synthesis, asymmetric catalysis, and drug discovery. Thus far, only a few catalytic asymmetric synthesis processes have been reported for assessing these stained atropisomers. In this study, we describe a highly enantioselective synthesis of monosubstituted [n]paracyclophanes by combining desymmetrization and kinetic resolution.
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