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<p>A pair of chiral organophosphorus iodide ligands, R/S-2’-(diphenylphosphaneyl)-[1,1’-binaphthalen]-2-yl)(methyl)diphenylphosphonium iodide (abbreviated as R/S-MBINAP<sup>+</sup>I<sup>−</sup>), was designedly synthesized to react with CuSCN, forming a pair of chiral iodo/thiocyano cuprous three-dimensional (3D) supramolecular frameworks, R/S-[Cu<sub>2</sub>(SCN)<sub>2</sub>I(MBINAP)]<sub>n</sub> (abbreviated as R/S-<b>1</b>). The 3D architectures were constructed by the connection of [Cu<sub>2</sub>(SCN)<sub>2</sub>]<sub>n</sub> chains with I<sup>−</sup> and R/S-MBINAP<sup>+</sup> ligands hanging on each side by coordination, through strong C–H···π interactions among the neighbouring chains, showing excellent thermal stability. R/S-<b>1</b> displayed characteristic chiral property of circular dichroism with mirror-symmetric cotton effect. Moreover, R-<b>1</b> exhibited fasinating ferroelectricity with <i>P</i><sub>r</sub> of 0.036 µC·cm<sup>− 2</sup>, <i>E</i><sub>c</sub> of 8.2&#xa0;kV·cm<sup>− 1</sup> and <i>P</i><sub>s</sub> of 0.13 µC·cm<sup>− 2</sup>. As expected, R/S-<b>1</b> showed luminescence with relatively long lifetime of 569 us (R-<b>1</b>) and 568 us (S-<b>1</b>). Furthermore, R/S-<b>1</b> exhibited good circular polarization luminescence (CPL) with <i>g</i><sub>lum</sub> being ± 3.0 × 10<sup>− 3</sup>. Theoretical calculations have been carried out to clarify the band structure of R-<b>1</b>. This work provides a new research strategy for the design and syntheses of chiral halogeno/pseudohalogeno cuprous polymers, and opens up a prospect for the multiple applications of chiral iodo/thiocyano cuprous materials.</p>

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Designed Syntheses of Chiral Iodo/Thiocyano Cuprous 3D Supramolecular Frameworks with Ferroelectricity and Circular Polarization Luminescence

  • 期刊论文

  • 发表日期：

    2025年2月19日

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  • Zhong-Xu Wang,
  • Wen-Xiang Chai,
  • Li Song

摘要

A pair of chiral organophosphorus iodide ligands, R/S-2’-(diphenylphosphaneyl)-[1,1’-binaphthalen]-2-yl)(methyl)diphenylphosphonium iodide (abbreviated as R/S-MBINAP+I−), was designedly synthesized to react with CuSCN, forming a pair of chiral iodo/thiocyano cuprous three-dimensional (3D) supramolecular frameworks, R/S-[Cu2(SCN)2I(MBINAP)]n (abbreviated as R/S-1). The 3D architectures were constructed by the connection of [Cu2(SCN)2]n chains with I− and R/S-MBINAP+ ligands hanging on each side by coordination, through strong C–H···π interactions among the neighbouring chains, showing excellent thermal stability. R/S-1 displayed characteristic chiral property of circular dichroism with mirror-symmetric cotton effect. Moreover, R-1 exhibited fasinating ferroelectricity with Pr of 0.036 µC·cm− 2, Ec of 8.2 kV·cm− 1 and Ps of 0.13 µC·cm− 2. As expected, R/S-1 showed luminescence with relatively long lifetime of 569 us (R-1) and 568 us (S-1). Furthermore, R/S-1 exhibited good circular polarization luminescence (CPL) with glum being ± 3.0 × 10− 3. Theoretical calculations have been carried out to clarify the band structure of R-1. This work provides a new research strategy for the design and syntheses of chiral halogeno/pseudohalogeno cuprous polymers, and opens up a prospect for the multiple applications of chiral iodo/thiocyano cuprous materials.