Alexander J Blake, Carlo Castellano, Vito Lippolis, Enrico Podda, Martin Schröder
{"title":"在大阳离子模板上形成扩展的聚碘化物。","authors":"Alexander J Blake, Carlo Castellano, Vito Lippolis, Enrico Podda, Martin Schröder","doi":"10.1107/S2053229624004194","DOIUrl":null,"url":null,"abstract":"<p><p>By studying the structures of (μ-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)bis[iodidopalladium(II)] diiodide penta(diiodine), [Pd<sub>2</sub>I<sub>2</sub>(C<sub>12</sub>H<sub>26</sub>N<sub>2</sub>S<sub>4</sub>)](I)<sub>2</sub>·5I<sub>2</sub> or [Pd<sub>2</sub>I<sub>2</sub>([18]aneN<sub>2</sub>S<sub>4</sub>)](I)<sub>2</sub>·(I<sub>2</sub>)<sub>5</sub>, and 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triiodide iodide hemipenta(diiodine) dichloromethane monosolvate, C<sub>18</sub>H<sub>38</sub>N<sub>2</sub>O<sub>6</sub><sup>2+</sup>·I<sub>3</sub><sup>-</sup>·I<sup>-</sup>·2.5I<sub>2</sub>·CH<sub>2</sub>Cl<sub>2</sub> or [H<sub>2</sub>([2.2.2]cryptand)](I<sub>3</sub>)(I)(I<sub>2</sub>)<sub>2.5</sub>·CH<sub>2</sub>Cl<sub>2</sub>, we confirm the structural variety of extended polyiodides achievable upon changing the shape, charge and dimensions of the cation template, by altering the synthetic strategy adopted and/or the experimental conditions. Although it is still often difficult to characterize discrete [I<sub>2m+n</sub>]<sup>n-</sup> polyiodides higher than I<sub>3</sub><sup>-</sup> on the basis of structural parameters, such as I-I bond distances, FT-Raman spectroscopy appears to identify them as aggregates of I<sub>2</sub>, I<sup>-</sup> and (symmetric or slightly asymmetric) I<sub>3</sub><sup>-</sup> building blocks linked by I...I interactions of varying strengths. However, because FT-Raman spectroscopy carries no information about the topological features of extended polyiodides, the two techniques should therefore be applied in combination to enhance the analysis of this kind of compounds.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":0.7000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11225612/pdf/","citationCount":"0","resultStr":"{\"title\":\"Formation of extended polyiodides at large cation templates.\",\"authors\":\"Alexander J Blake, Carlo Castellano, Vito Lippolis, Enrico Podda, Martin Schröder\",\"doi\":\"10.1107/S2053229624004194\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>By studying the structures of (μ-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)bis[iodidopalladium(II)] diiodide penta(diiodine), [Pd<sub>2</sub>I<sub>2</sub>(C<sub>12</sub>H<sub>26</sub>N<sub>2</sub>S<sub>4</sub>)](I)<sub>2</sub>·5I<sub>2</sub> or [Pd<sub>2</sub>I<sub>2</sub>([18]aneN<sub>2</sub>S<sub>4</sub>)](I)<sub>2</sub>·(I<sub>2</sub>)<sub>5</sub>, and 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triiodide iodide hemipenta(diiodine) dichloromethane monosolvate, C<sub>18</sub>H<sub>38</sub>N<sub>2</sub>O<sub>6</sub><sup>2+</sup>·I<sub>3</sub><sup>-</sup>·I<sup>-</sup>·2.5I<sub>2</sub>·CH<sub>2</sub>Cl<sub>2</sub> or [H<sub>2</sub>([2.2.2]cryptand)](I<sub>3</sub>)(I)(I<sub>2</sub>)<sub>2.5</sub>·CH<sub>2</sub>Cl<sub>2</sub>, we confirm the structural variety of extended polyiodides achievable upon changing the shape, charge and dimensions of the cation template, by altering the synthetic strategy adopted and/or the experimental conditions. Although it is still often difficult to characterize discrete [I<sub>2m+n</sub>]<sup>n-</sup> polyiodides higher than I<sub>3</sub><sup>-</sup> on the basis of structural parameters, such as I-I bond distances, FT-Raman spectroscopy appears to identify them as aggregates of I<sub>2</sub>, I<sup>-</sup> and (symmetric or slightly asymmetric) I<sub>3</sub><sup>-</sup> building blocks linked by I...I interactions of varying strengths. However, because FT-Raman spectroscopy carries no information about the topological features of extended polyiodides, the two techniques should therefore be applied in combination to enhance the analysis of this kind of compounds.</p>\",\"PeriodicalId\":7115,\"journal\":{\"name\":\"Acta Crystallographica Section C Structural Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11225612/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Crystallographica Section C Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2053229624004194\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/5/13 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section C Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2053229624004194","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/5/13 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Formation of extended polyiodides at large cation templates.
By studying the structures of (μ-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)bis[iodidopalladium(II)] diiodide penta(diiodine), [Pd2I2(C12H26N2S4)](I)2·5I2 or [Pd2I2([18]aneN2S4)](I)2·(I2)5, and 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triiodide iodide hemipenta(diiodine) dichloromethane monosolvate, C18H38N2O62+·I3-·I-·2.5I2·CH2Cl2 or [H2([2.2.2]cryptand)](I3)(I)(I2)2.5·CH2Cl2, we confirm the structural variety of extended polyiodides achievable upon changing the shape, charge and dimensions of the cation template, by altering the synthetic strategy adopted and/or the experimental conditions. Although it is still often difficult to characterize discrete [I2m+n]n- polyiodides higher than I3- on the basis of structural parameters, such as I-I bond distances, FT-Raman spectroscopy appears to identify them as aggregates of I2, I- and (symmetric or slightly asymmetric) I3- building blocks linked by I...I interactions of varying strengths. However, because FT-Raman spectroscopy carries no information about the topological features of extended polyiodides, the two techniques should therefore be applied in combination to enhance the analysis of this kind of compounds.
期刊介绍：
Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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