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<p>We reported the rational design and synthesis of a novel series of heteroleptic Cu(I) complexes L<sup>n</sup>CuX(Phen) (n = 1, X = Cl (<b>1a</b>), Br (<b>1b</b>), I (<b>1c</b>); n = 2, X = Cl (<b>2a</b>), Br (<b>2b</b>), I (<b>2c</b>); n = 3, X = Cl (<b>3a</b>), Br (<b>3b</b>), I (<b>3c</b>); where L<sup>n</sup> = NPN = PhP(C<sub>6</sub>H<sub>4</sub>-2-HC = NAr)<sub>2</sub> (Ar = 4-OMeC<sub>6</sub>H<sub>4</sub> (L<sup>1</sup>, <b>1</b>), 4-ClC<sub>6</sub>H<sub>4</sub> (L<sup>2</sup>, <b>2</b>), 4-BrC<sub>6</sub>H<sub>4</sub> (L<sup>3</sup>, <b>3</b>)), Phen = NN = <i>o</i>-phenanthroline), which represent the first systematic exploration of this type of NPN-NN hybrid coordination spheres in Cu(I) chemistry. These complexes were characterized using melting point analysis, FT-IR, <sup>1</sup>H/<sup>13</sup>C/<sup>31</sup>P NMR spectroscopy, and single-crystal X-ray diffraction, revealing the tetra-coordinate geometry at Cu(I) centers stabilized by synergistic P-donor (from NPN) and N-donor (from Phen) ligands. Structural analysis uncovered the inter/intramolecular π-π interactions and intermolecular C-H···π interactions that dictate their solid-state assembly and properties. While catalytic evaluation in Chan-Lam reactions showed moderated activity of NPN-NN heteroleptic Cu(I) complexes compared to monoleptic NPN-Cu analogues [L<sup>n</sup>CuX]<sub>m</sub> (m = 1, 2, 4), this study provides foundational insights into how ligand cooperativity influences reactivity. Notably, the title complexes exhibit tunable photoluminescence in the solid state (581–648 nm) and solution (519–525&#xa0;nm), highlighting their potential as emissive materials.</p>

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Heteroleptic Cu(I) complexes with Bis(imino)phosphine and o-phenanthroline: structure and photophysical and catalytic properties

  • 期刊论文

  • 发表日期：

    2026年7月20日

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  • Shuai-cong Huo,
  • Xu-yan Bai,
  • Li-ping Chen,
  • Yu-jia Gao,
  • Ying Yang

摘要

We reported the rational design and synthesis of a novel series of heteroleptic Cu(I) complexes LnCuX(Phen) (n = 1, X = Cl (1a), Br (1b), I (1c); n = 2, X = Cl (2a), Br (2b), I (2c); n = 3, X = Cl (3a), Br (3b), I (3c); where Ln = NPN = PhP(C6H4-2-HC = NAr)2 (Ar = 4-OMeC6H4 (L1, 1), 4-ClC6H4 (L2, 2), 4-BrC6H4 (L3, 3)), Phen = NN = o-phenanthroline), which represent the first systematic exploration of this type of NPN-NN hybrid coordination spheres in Cu(I) chemistry. These complexes were characterized using melting point analysis, FT-IR, 1H/13C/31P NMR spectroscopy, and single-crystal X-ray diffraction, revealing the tetra-coordinate geometry at Cu(I) centers stabilized by synergistic P-donor (from NPN) and N-donor (from Phen) ligands. Structural analysis uncovered the inter/intramolecular π-π interactions and intermolecular C-H···π interactions that dictate their solid-state assembly and properties. While catalytic evaluation in Chan-Lam reactions showed moderated activity of NPN-NN heteroleptic Cu(I) complexes compared to monoleptic NPN-Cu analogues [LnCuX]m (m = 1, 2, 4), this study provides foundational insights into how ligand cooperativity influences reactivity. Notably, the title complexes exhibit tunable photoluminescence in the solid state (581–648 nm) and solution (519–525 nm), highlighting their potential as emissive materials.