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We report the synthesis of chiral lanthanide complexes with extended π conjugation for efficient circularly polarized luminescence (CPL) via two-photon excitation (2PE). The pyridine bis-oxazoline (PyBox) core provides the chiral Ln environment, while the extension of the conjugated backbone through the pyridine 4-position with a phenylacetylene unit increases the two-photon absorption cross section. This work presents an important step toward the development of chiral systems displaying enhanced nonlinear optical properties, with potential applications in imaging and sensing, as well as in photodynamic therapy due to the selective excitation of molecules within a specific focal volume.
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http://dx.doi.org/10.1021/jacs.3c05957 | DOI Listing |
J Phys Condens Matter
December 2024
Department of Physics and Astronomy, University of Nebraska-Lincoln, Jorgenesen Hall, 855 North 16th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
Evidence of chirality was observed at the Fe metal center in Fe(III) spin crossover coordination salts [Fe(qsal)Ni(dmit)] and [Fe(qsal)(TCNQ)] from X-ray absorption spectroscopy at the Fe 2pcore threshold. Based on the circularly polarized X-ray absorption data, the X-ray natural circular dichroism seen [Fe(qsal)Ni(dmit)] and [Fe(qsal)(TCNQ)] is far stronger than seen for [Fe(qsal)Cl] suggesting this natural circular dichroism signature is a ligand effect rather than a result of just a loss of octahedral symmetry on the Fe core. The larger the chiral effects in the Fe 2p core to bound X-ray absorption, the greater the perturbation of the Fe 2pto 2pspin-orbit splitting seen in the X-ray absorption spectra.
View Article and Find Full Text PDFJ Chem Theory Comput
December 2024
Department of Physics, School of Physical Science and Technology, Ningbo University, Ningbo 315211, P.R. China.
The evolution of photosynthetic reaction centers (RCs) from anoxygenic bacteria to higher-order oxygenic cynobacteria and plants highlights a remarkable journey of structural and functional diversification as an adaptation to environmental conditions. The role of chirality in these centers is important, influencing the arrangement and function of key molecules involved in photosynthesis. Investigating the role of chirality may provide a deeper understanding of photosynthesis and the evolutionary history of life on Earth.
View Article and Find Full Text PDFChemistry
December 2024
Tongji University, School of Chemical Science and Engineering, 1239 Siping Road, Shanghai, CHINA.
Upconverted circularly polarized luminescence (UC-CPL) active organic and organic-inorganic composite materials have garnered increasing attention due to their vast potential applications in areas such as 3D displays, encryptions, spintronics and optoelectronic devices. However, effective methods for fabricating chiral inorganic materials exhibiting UC-CPL remain a challenge. Herein, we propose an approach for the synthesis of UC-CPL active chiral mesostructured CeO2 powders (CMCs) via a hydrothermal growth method, using L/D-aspartic acid as symmetry-breaking and structure-directing agents.
View Article and Find Full Text PDFPhys Rev Lett
December 2024
Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom.
We have measured the spin polarization of a slow positron beam via state-selective depopulation of 2^{3}S_{1} positronium atoms, generated by passing the beam through a gas cell. Our method employs circularly polarized microwave radiation to drive 2^{3}S_{1}→2^{3}P_{1} transitions, for which either Δm_{J}=+1 or Δm_{J}=-1, and relies on the fact that asymmetries between the two cases yield the underlying positron beam polarization. Using this technique we show that the polarization of a positron beam derived from a solid neon moderator may be increased from 30% to 90% by increasing the moderator thickness, with an associated reduction in beam intensity of 60%.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Shanghai Jiaotong University: Shanghai Jiao Tong University, School of Chemistry and Chemical Engineeringg, Dongchuan Road, Num 800, 200092, Shanghai, CHINA.
Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three-dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non-contact modulation of CPL remain challenging. In this work, color-switchable homochiral CPL films with high luminescence asymmetry factor (glum~0.
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