Anastassiades Antonis, Alexandropoulos Dimitris I, Hale Ashlyn, Christou George, Perlepes Spyros P, Tasiopoulos Anastasios J
Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus.
Department of Chemistry, University of Patras, 26504 Patras, Greece.
Cryst Growth Des. 2024 Oct 9;24(21):9076-9083. doi: 10.1021/acs.cgd.4c01100. eCollection 2024 Nov 6.
The initial use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH) in Mn cluster chemistry has afforded two new mixed-valence polynuclear Mn clusters, namely, [MnΟ(pypd)(hmp)(OCCMe)] () and [MnΟ(N)(pypd){(py)CO}(OCEt)] () (hmp = deprotonated 2-hydroxymethylpyridine; (py)CO = deprotonated gem-diol form of di-2-pyridyl ketone). Compound features a novel [Mn Mn(μ-O)(μ-O)(μ-OR)] structural core resembling a supertetrahedron T3, lacking two apexes, while complex has a [Mn Mn (μ-O)(μ-O)(μ-N)(μ-OR)(μ-OR)] core consisting of two [Mn] subunits related to and thus is a dimeric analogue of . Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes and and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH to stabilize high nuclearity 3d metal clusters based on polynuclear building blocks.
2-(吡啶-2-基)丙烷-1,3-二醇(pypdH)在锰簇化学中的首次应用得到了两种新的混合价多核锰簇，即MnΟ(pypd)(hmp)(OCCMe)和MnΟ(N)(pypd){(py)CO}(OCEt)(hmp = 去质子化的2-羟甲基吡啶；(py)CO = 二-2-吡啶基酮的去质子化偕二醇形式)。化合物具有一个类似于超级四面体T3的新型[Mn Mn(μ-O)(μ-O)(μ-OR)]结构核心，缺少两个顶点，而配合物具有一个由两个与相关的[Mn]亚基组成的[Mn Mn (μ-O)(μ-O)(μ-N)(μ-OR)(μ-OR)]核心，因此是化合物的二聚类似物。直流(DC)磁化率研究表明，配合物和中的锰离子之间存在主要的反铁磁交换相互作用，且两种化合物的基态自旋值都很小。总的来说，这项工作突出了像pypdH这样的多元醇类螯合物基于多核结构单元稳定高核3d金属簇的能力。
