Matthew P Snelgrove, Natalia N Sergeeva, Michaele J Hardie
{"title":"由铜（II）氯化物簇连接的高配位笼型链烷：网络和转化。","authors":"Matthew P Snelgrove, Natalia N Sergeeva, Michaele J Hardie","doi":"10.1002/chem.202403692","DOIUrl":null,"url":null,"abstract":"<p><p>Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>} cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>2</sub> cage-catenane through a planar, linear tetranuclear {Cu<sub>4</sub>(μ-Cl)<sub>6</sub>Cl<sub>2</sub>} cluster. The complex of discrete tetrameric {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>4</sub> assemblies (dimers of cage-catenanes) transforms through solvent-exchange processes to 1D coordination chain structures through additional {Cu<sub>2</sub>(μ-Cl)<sub>2</sub>} bridges between the tetrameric {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>4</sub> assemblies. Complex [Cu<sub>6</sub>(L1)<sub>4</sub>Cl<sub>12</sub>(H<sub>2</sub>O)<sub>3</sub>] ⋅ (H<sub>2</sub>O) ⋅ 15(DMF) C2 features a 2D coordination network of 6<sup>3</sup> topology linked through three different Cu(II) clusters, namely {Cu<sub>4</sub>(μ-Cl)<sub>6</sub>}, {Cu<sub>2</sub>(μ-Cl)<sub>2</sub>} and a rare linear {Cu<sub>2</sub>(μ-Cl)} linkage. Break-down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu-Cl-Cl bond.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403692"},"PeriodicalIF":3.9000,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Higher Assemblies of Coordination Cage-Catenanes Linked by Copper(II) Chloride Clusters: Networks and Transformations.\",\"authors\":\"Matthew P Snelgrove, Natalia N Sergeeva, Michaele J Hardie\",\"doi\":\"10.1002/chem.202403692\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>} cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>2</sub> cage-catenane through a planar, linear tetranuclear {Cu<sub>4</sub>(μ-Cl)<sub>6</sub>Cl<sub>2</sub>} cluster. The complex of discrete tetrameric {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>4</sub> assemblies (dimers of cage-catenanes) transforms through solvent-exchange processes to 1D coordination chain structures through additional {Cu<sub>2</sub>(μ-Cl)<sub>2</sub>} bridges between the tetrameric {Cu<sub>3</sub>(L1)<sub>2</sub>(X)<sub>6</sub>}<sub>4</sub> assemblies. Complex [Cu<sub>6</sub>(L1)<sub>4</sub>Cl<sub>12</sub>(H<sub>2</sub>O)<sub>3</sub>] ⋅ (H<sub>2</sub>O) ⋅ 15(DMF) C2 features a 2D coordination network of 6<sup>3</sup> topology linked through three different Cu(II) clusters, namely {Cu<sub>4</sub>(μ-Cl)<sub>6</sub>}, {Cu<sub>2</sub>(μ-Cl)<sub>2</sub>} and a rare linear {Cu<sub>2</sub>(μ-Cl)} linkage. Break-down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu-Cl-Cl bond.</p>\",\"PeriodicalId\":144,\"journal\":{\"name\":\"Chemistry - A European Journal\",\"volume\":\" \",\"pages\":\"e202403692\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-01-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry - A European Journal\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/chem.202403692\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/12/19 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - A European Journal","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/chem.202403692","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/12/19 0:00:00","PubModel":"Epub","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Higher Assemblies of Coordination Cage-Catenanes Linked by Copper(II) Chloride Clusters: Networks and Transformations.
Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu3(L1)2(X)6} cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu3(L1)2(X)6}2 cage-catenane through a planar, linear tetranuclear {Cu4(μ-Cl)6Cl2} cluster. The complex of discrete tetrameric {Cu3(L1)2(X)6}4 assemblies (dimers of cage-catenanes) transforms through solvent-exchange processes to 1D coordination chain structures through additional {Cu2(μ-Cl)2} bridges between the tetrameric {Cu3(L1)2(X)6}4 assemblies. Complex [Cu6(L1)4Cl12(H2O)3] ⋅ (H2O) ⋅ 15(DMF) C2 features a 2D coordination network of 63 topology linked through three different Cu(II) clusters, namely {Cu4(μ-Cl)6}, {Cu2(μ-Cl)2} and a rare linear {Cu2(μ-Cl)} linkage. Break-down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu-Cl-Cl bond.
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