A [Mn8] Defective Supertetrahedron T3 and Its Dimeric [Mn16] Analogue

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-10-09 DOI:10.1021/acs.cgd.4c0110010.1021/acs.cgd.4c01100

Antonis Anastassiades, Dimitris I. Alexandropoulos, Ashlyn Hale, George Christou, Spyros P. Perlepes and Anastasios J. Tasiopoulos*,

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引用次数: 0

Abstract

The initial use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH₂) in Mn cluster chemistry has afforded two new mixed-valence polynuclear Mn clusters, namely, [Mn₈Ο₅(pypd)(hmp)₃(O₂CCMe₃)₈] (1) and [Mn₁₆Ο₁₀(N₃)₂(pypd)₂{(py)₂CO₂}₄(O₂CEt)₁₂] (2) (hmp^– = deprotonated 2-hydroxymethylpyridine; (py)₂CO₂^2– = deprotonated gem-diol form of di-2-pyridyl ketone). Compound 1 features a novel [Mn^III₇Mn^II(μ₄-O)₂(μ₃-O)₃(μ-OR)₅]⁸⁺ structural core resembling a supertetrahedron T3, lacking two apexes, while complex 2 has a [Mn^III₁₄Mn^II₂(μ₄-O)₄(μ₃-O)₆(μ-N₃)₂(μ₃-OR)₂(μ-OR)₈]¹⁴⁺ core consisting of two [Mn₈] subunits related to 1 and thus is a dimeric analogue of 1. Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes 1 and 2 and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH₂ to stabilize high nuclearity 3d metal clusters based on polynuclear building blocks.

The initial use of 2-(pyridin-2-yl)propane-1,3-diol ligand in Mn cluster chemistry has afforded two new polynuclear [Mn₈] and [Mn₁₆] clusters. They feature novel, structurally related [Mn^III₇Mn^II(μ₄-O)₂(μ₃-O)₃(μ-OR)₅]⁸⁺ (1) and [Mn^III₁₄Mn^II₂(μ₄-O)₄(μ₃-O)₆(μ-N₃)₂(μ₃-OR)₂(μ-OR)₈]¹⁴⁺ (2) cores consisting of one and two (connected) defective supertetrahedra T3, lacking two apexes, respectively. Magnetism studies revealed dominant antiferromagentic exchange interactions and small spin ground state values for both compounds.

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一种[Mn8] 缺陷超四面体 T3 及其二聚体[Mn16] 类似物

将 2-(吡啶-2-基)丙烷-1,3-二醇（pypdH2）首次用于锰簇化学反应中，产生了两种新的混合价多核锰簇、即 [Mn8Ο5(pypd)(hmp)3(O2CCMe3)8] (1) 和 [Mn16Ο10(N3)2(pypd)2{(py)2CO2}4(O2CEt)12] (2) （hmp- = 去质子化的 2-羟甲基吡啶；(py)2CO22- = 二-2-吡啶基酮的去质子化 gem-diol 形式）。化合物 1 具有新颖的[MnIII7MnII(μ4-O)2(μ3-O)3(μ-OR)5]8+结构核心，类似于缺乏两个顶点的超四面体 T3、而复合物 2 具有一个[MnIII14MnII2(μ4-O)4(μ3-O)6(μ-N3)2(μ3-OR)2(μ-OR)8]14+ 核心，由与 1 有关的两个[Mn8]亚基组成，因此是 1 的二聚类似物。直流磁感应强度研究表明，复合物 1 和 2 中的锰离子之间存在主要的反铁磁交换相互作用，而且这两种化合物的基态自旋值都很小。总之，这项工作突出了多元醇类螯合物（如 pypdH2）稳定基于多核结构单元的高核度 3d 金属簇的能力。它们具有结构相关的新型[MnIII7MnII(μ4-O)2(μ3-O)3(μ-OR)5]8+ (1)和[MnIII14MnII2(μ4-O)4(μ3-O)6(μ-N3)2(μ3-OR)2(μ-OR)8]14+ (2)核心，分别由一个和两个（相连）缺顶的缺陷超四面体 T3 组成。磁性研究表明，这两种化合物的反铁磁交换相互作用占主导地位，自旋基态值较小。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.