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Updated: Aug 15, 2025

Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
Published on: April 14, 2020
Enhanced circularly polarized luminescence of chiral Eu(III) coordination polymers with structural strain
Makoto Tsurui1, Yuichi Kitagawa2, Sunao Shoji2,3
1Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-8628, Japan.
Abstract:
Three types of Eu(III) coordination polymers with different distorted chiral ligands, [Eu(+tfc)3(p-dpeb)], [Eu(+pfc)3(p-dpeb)], and [Eu(+hfc)3(p-dpeb)] (+tfc: (+)-3-(trifluoroacetyl)camphorate, +pfc: (+)-3-(pentafluoropropionyl)camphorate, +hfc: (+)-3-(heptafluorobutyryl)camphorate, p-dpeb: 1,4-bis(diphenylphosphorylethynyl)benzene), were prepared for elucidating the relationship between their structural distortions, ligand-to-metal charge transfer (LMCT), and circularly polarized luminescence (CPL) properties. Their strain factors in the ligands were evaluated using crystallographic data obtained by single-crystal X-ray structural analyses. The characteristics of the LMCT excited states were estimated from theoretical calculations. The introduction of a bulky substituent into the chiral ligand afforded a distorted structure of β-diketonates and changed the direction of the transition electric dipole moments, which are related to the magnitude of the CPL intensity. The CPL dissymmetry factor (gCPL) of [Eu(+hfc)3(p-dpeb)], with a large distorted structure, was -0.22, while those of [Eu(+tfc)3(p-dpeb)] and [Eu(+pfc)3(p-dpeb)], with small distorted structures, were -0.05 and -0.10, respectively. The controlled steric hindrance of the chiral ligands in Eu(III) coordination polymers is one of the strain factors enhancing their CPL properties.
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