取代基操纵构建的镧系元素分子团簇和金属有机层

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-02-05 DOI:10.1021/acs.inorgchem.4c04885

Yun-Lan Li, Hai-Fang Lan, Hai-Ling Wang, Zhong-Hong Zhu, Lei Cheng, Hua-Hong Zou

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引用次数: 0

摘要

通常，通过调节取代基来构建不同连接和形状的配合物。然而，仅通过微调配体的取代基，特别是具有相似物理化学性质的取代基（−CH3和−CH2CH3）来构建两种不同尺寸的镧系配合物是极具挑战性的。本文在多齿螯合配位法（MCC）的指导下，通过仅调节多齿螯合配体的取代基，采用多组分“一锅法”成功构建了两个不同尺寸和连接方式的镧系配合物。它们是11核镧系元素分子团簇（Dy11）和金属有机层（2D-Dy）。具体来说，当选择的配体是咪唑-2-羧醛衍生物，其取代基是−CH3时，得到层状的2D-Dy。具有螺旋桨构型的连接剂[Dy(HL1)3]是由Dy（III）离子与三个水杨酰肼和1-甲基- 1h -咪唑-2-甲醛缩合形成的酰基腙配体（HL1）螯合而成的。进一步以螺旋桨状的[Dy(NO3)3]作为二次构建单元（SBU）进行交替连接，形成2D-Dy。此外，通过将配体上的−CH3改变为−CH2CH3，我们得到了以沙漏形Dy9为核心，由两个Dy（III）离子外延组装而成的Dy11的例子，其分子式为[Dy11(HL2)8(μ3-OH)8(μ4-O)2(ch30)4(NO3)4](NO3)5 18CH3OH。利用高分辨率电喷雾质谱（HRESI-MS）对簇Dy11进行轰击，并捕获了形成的各种片段的分子离子峰。根据上述分子离子峰，推测Dy11可能的破碎机制为Dy11→Dy4(HL2)4→Dy3(HL2)2→Dy2(HL2)2→Dy(HL2)2和Dy11→Dy(HL2)2/Dy2(HL2)2/Dy3(HL2)2/Dy4(HL2)4。这项工作是罕见的配体取代基微调导致不同尺寸配合物形成的例子之一，促进了镧系配合物晶体工程的进展。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Lanthanide Molecular Clusters and Metal–Organic Layers Constructed by Manipulation of Substituents

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Lanthanide Molecular Clusters and Metal–Organic Layers Constructed by Manipulation of Substituents

Usually, complexes with different connections and shapes are constructed by regulating the substituents. However, it is extremely challenging to construct two lanthanide complexes with different dimensions by only fine-tuning the substituents of the ligands, especially the substituents (−CH₃ and −CH₂CH₃) with almost similar physical and chemical properties. Herein, by only regulating the substituents of the multidentate chelating ligands, two lanthanide complexes with different dimensions and connection modes were successfully constructed using a multicomponent “one-pot method” under the guidance of the multidentate chelating coordination method (MCC). They are the 11-nuclear lanthanide molecular cluster (Dy₁₁) and the metal–organic layer (2D-Dy). Specifically, when the selected ligand is an imidazole-2-carboxaldehyde derivative and its substituent is −CH₃, a layered 2D-Dy is obtained. The linker [Dy(HL¹)₃] with a propeller configuration is formed by chelating the Dy(III) ion with an acylhydrazone ligand (HL¹) formed by the condensation of three salicylhydrazides and 1-methyl-1H-imidazole-2-carboxaldehyde. The above linkers were further linked alternately with propeller-shaped [Dy(NO₃)₃] as a secondary building unit (SBU) to form 2D-Dy. In addition, by changing the −CH₃ on the ligand to −CH₂CH₃, we obtained an example of Dy₁₁ formed by epitaxial assembly of two Dy(III) ions with an hourglass-shaped Dy₉ as the core, and its molecular formula is [Dy₁₁(HL²)₈(μ₃–OH)₈(μ₄-O)₂(CH₃O)₄(NO₃)₄](NO₃)₅ 18CH₃OH. The cluster Dy₁₁ was bombarded using high-resolution electrospray ionization mass spectrometry (HRESI-MS) and the molecular ion peaks of various fragments formed were captured. Based on the above molecular ion peaks, the possible fragmentation mechanisms of Dy₁₁ were inferred to be Dy₁₁ → Dy₄(HL²)₄ → Dy₃(HL²)₂ → Dy₂(HL²)₂ → Dy(HL²)₂ and Dy₁₁ → Dy(HL²)₂/Dy₂(HL²)₂/Dy₃(HL²)₂/Dy₄(HL²)₄. This work is one of the rare examples where fine-tuning of ligand substituents leads to the formation of complexes of different dimensions, which promotes the progress of crystal engineering of lanthanide complexes.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.