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 eCollection Date: 2024-11-06 DOI:10.1021/acs.cgd.4c01100

Antonis Anastassiades, Dimitris I Alexandropoulos, Ashlyn Hale, George Christou, Spyros P Perlepes, 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^III ₇Mn^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^III ₁₄Mn^II ₂(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.

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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)2CO2 2- = 二-2-吡啶基酮的去质子化 gem-diol 形式）。化合物 1 具有新颖的[MnIII 7MnII(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[MnIII 14MnII 2(μ4-O)4(μ3-O)6(μ-N3)2(μ3-OR)2(μ-OR)8]14+ 核，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）稳定基于多核构建模块的高核度 3d 金属簇的能力。

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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.