Using NaN₃ and a chiral N-donor ligand (1R,2R)-1,2-diphenylethylenediamine (L) to react with Co(ClO₄)₂(H₂O)₆ and Ni(ClO₄)₂(H₂O)₆, respectively, two chiral Co^III and Ni^II complexes with formulae [Co(L)₂(N₃)₂](ClO₄)(0.5H₂O) (1) and [Ni(L)₂(μ_1,3-N₃)]_n(ClO₄)_n(0.5H₂O)_n (2) were isolated and structurally characterized. Although 1 and 2 contain the same L and N₃⁻ ligands, they have completely different molecular structures. 1 shows a chiral mononuclear structure with N₃⁻ as the terminal ligand, in which the Co^II ion has been oxidized to the Co^III ion, while 2 exhibits a chiral one-dimensional (1D) Ni^II chain structure with N₃⁻ as the bridging ligand. Notably, a study of their nonlinear optical (NLO) properties demonstrates that 1 presents a moderate second-harmonic generation (SHG) response (0.15 × KDP), while 2 only displays a strong third-harmonic generation (THG) response (160 × α-SiO₂). This interesting finding gives the first example of the complexes with the same ligands but different molecular structures showing completely different NLO responses regulated by metal ions.

中文翻译：

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具有相同配体的两种手性 CoIII 和 NiII 配合物呈现不同的非线性光学响应


使用NaN ₃ 和手性N-供体配体(1R,2R)-1,2-二苯基乙二胺(L)与Co(ClO ₄ ) ₂ O) ₆ 和 Ni(ClO ₄ ) ₂ (H ₂ O) < b8> 分别是两个手性 Co ^III 和 Ni ^II 配合物，其化学式为 [Co(L) ₂ (N ₃ ](ClO ₄ )(0.5H ₂ O) (1) 和 [Ni(L) ₂ ( μ _1,3 -N ₃ )] _n (ClO ₄ ) _n (0.5H ₂ (2) 被分离并进行结构表征。虽然1和2含有相同的L和N ₃ ⁻ 配体，但它们具有完全不同的分子结构。图1为以N ₃ ⁻ 为末端配体的手性单核结构，其中Co ^II 离子已被氧化为Co ^III 链结构，以N ₃ ⁻ 作为桥联配体。值得注意的是，对其非线性光学 (NLO) 特性的研究表明，1 呈现中等的二次谐波产生 (SHG) 响应 (0.15 × KDP)，而 2 只表现出较强的三次谐波产生 (THG) 响应 (160 × α -SiO ₂ ）。这一有趣的发现给出了具有相同配体但不同分子结构的配合物的第一个例子，显示出受金属离子调节的完全不同的 NLO 响应。