Antonis Anastassiades, Dimitris I Alexandropoulos, Ashlyn Hale, George Christou, Spyros P Perlepes, Anastasios J Tasiopoulos
{"title":"一种[Mn8] 缺陷超四面体 T3 及其二聚体[Mn16] 类似物。","authors":"Antonis Anastassiades, Dimitris I Alexandropoulos, Ashlyn Hale, George Christou, Spyros P Perlepes, Anastasios J Tasiopoulos","doi":"10.1021/acs.cgd.4c01100","DOIUrl":null,"url":null,"abstract":"<p><p>The initial use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH<sub>2</sub>) in Mn cluster chemistry has afforded two new mixed-valence polynuclear Mn clusters, namely, [Mn<sub>8</sub>Ο<sub>5</sub>(pypd)(hmp)<sub>3</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>] (<b>1</b>) and [Mn<sub>16</sub>Ο<sub>10</sub>(N<sub>3</sub>)<sub>2</sub>(pypd)<sub>2</sub>{(py)<sub>2</sub>CO<sub>2</sub>}<sub>4</sub>(O<sub>2</sub>CEt)<sub>12</sub>] (<b>2</b>) (hmp<sup>-</sup> = deprotonated 2-hydroxymethylpyridine; (py)<sub>2</sub>CO<sub>2</sub> <sup>2-</sup> = deprotonated gem-diol form of di-2-pyridyl ketone). Compound <b>1</b> features a novel [Mn<sup>III</sup> <sub>7</sub>Mn<sup>II</sup>(μ<sub>4</sub>-O)<sub>2</sub>(μ<sub>3</sub>-O)<sub>3</sub>(μ-OR)<sub>5</sub>]<sup>8+</sup> structural core resembling a supertetrahedron T3, lacking two apexes, while complex <b>2</b> has a [Mn<sup>III</sup> <sub>14</sub>Mn<sup>II</sup> <sub>2</sub>(μ<sub>4</sub>-O)<sub>4</sub>(μ<sub>3</sub>-O)<sub>6</sub>(μ-N<sub>3</sub>)<sub>2</sub>(μ<sub>3</sub>-OR)<sub>2</sub>(μ-OR)<sub>8</sub>]<sup>14+</sup> core consisting of two [Mn<sub>8</sub>] subunits related to <b>1</b> and thus is a dimeric analogue of <b>1</b>. Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes <b>1</b> and <b>2</b> and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH<sub>2</sub> to stabilize high nuclearity 3d metal clusters based on polynuclear building blocks.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 21","pages":"9076-9083"},"PeriodicalIF":3.2000,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11555654/pdf/","citationCount":"0","resultStr":"{\"title\":\"A [Mn<sub>8</sub>] Defective Supertetrahedron T3 and Its Dimeric [Mn<sub>16</sub>] Analogue.\",\"authors\":\"Antonis Anastassiades, Dimitris I Alexandropoulos, Ashlyn Hale, George Christou, Spyros P Perlepes, Anastasios J Tasiopoulos\",\"doi\":\"10.1021/acs.cgd.4c01100\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The initial use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH<sub>2</sub>) in Mn cluster chemistry has afforded two new mixed-valence polynuclear Mn clusters, namely, [Mn<sub>8</sub>Ο<sub>5</sub>(pypd)(hmp)<sub>3</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>] (<b>1</b>) and [Mn<sub>16</sub>Ο<sub>10</sub>(N<sub>3</sub>)<sub>2</sub>(pypd)<sub>2</sub>{(py)<sub>2</sub>CO<sub>2</sub>}<sub>4</sub>(O<sub>2</sub>CEt)<sub>12</sub>] (<b>2</b>) (hmp<sup>-</sup> = deprotonated 2-hydroxymethylpyridine; (py)<sub>2</sub>CO<sub>2</sub> <sup>2-</sup> = deprotonated gem-diol form of di-2-pyridyl ketone). Compound <b>1</b> features a novel [Mn<sup>III</sup> <sub>7</sub>Mn<sup>II</sup>(μ<sub>4</sub>-O)<sub>2</sub>(μ<sub>3</sub>-O)<sub>3</sub>(μ-OR)<sub>5</sub>]<sup>8+</sup> structural core resembling a supertetrahedron T3, lacking two apexes, while complex <b>2</b> has a [Mn<sup>III</sup> <sub>14</sub>Mn<sup>II</sup> <sub>2</sub>(μ<sub>4</sub>-O)<sub>4</sub>(μ<sub>3</sub>-O)<sub>6</sub>(μ-N<sub>3</sub>)<sub>2</sub>(μ<sub>3</sub>-OR)<sub>2</sub>(μ-OR)<sub>8</sub>]<sup>14+</sup> core consisting of two [Mn<sub>8</sub>] subunits related to <b>1</b> and thus is a dimeric analogue of <b>1</b>. Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagentic exchange interactions between the Mn ions in complexes <b>1</b> and <b>2</b> and small ground state spin values for both compounds. Overall, this work highlights the capability of polyol-like chelates like pypdH<sub>2</sub> to stabilize high nuclearity 3d metal clusters based on polynuclear building blocks.</p>\",\"PeriodicalId\":34,\"journal\":{\"name\":\"Crystal Growth & Design\",\"volume\":\"24 21\",\"pages\":\"9076-9083\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-10-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11555654/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Crystal Growth & Design\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.cgd.4c01100\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/11/6 0:00:00\",\"PubModel\":\"eCollection\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.cgd.4c01100","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/11/6 0:00:00","PubModel":"eCollection","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
A [Mn8] Defective Supertetrahedron T3 and Its Dimeric [Mn16] Analogue.
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)2CO22- = deprotonated gem-diol form of di-2-pyridyl ketone). Compound 1 features a novel [MnIII7MnII(μ4-O)2(μ3-O)3(μ-OR)5]8+ structural core resembling a supertetrahedron T3, lacking two apexes, while complex 2 has a [MnIII14MnII2(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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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.
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