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

IF 4.3 3区材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC

ACS Applied Electronic Materials 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。

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来源期刊

ACS Applied Electronic Materials Multiple-

CiteScore

7.20

自引率

4.30%

发文量

567