{"title":"基于 1,1'-(5-甲基-1,3-亚苯基)双(1H-咪唑)配体的六方棱柱形金属有机笼和金属有机聚合物：合成、结构表征和磁性能","authors":"","doi":"10.1016/j.jssc.2024.124974","DOIUrl":null,"url":null,"abstract":"<div><p>A serial of hexagonal-prismatic metal organic cages (MOCs), [Co<sub>6</sub>(OH)<sub>2</sub>(HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·SO<sub>4</sub>·2HCOO·8H<sub>2</sub>O (<strong>1</strong>·2HCOO·8H<sub>2</sub>O), [Ni<sub>6</sub>(OH)<sub>2</sub>(HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·SO<sub>4</sub>·2HCOO·8H<sub>2</sub>O (<strong>2</strong>·HCOO·8H<sub>2</sub>O), {[Co<sub>6</sub>(<em>μ</em><sub>3</sub>-OH)<sub>2</sub>(<em>μ-</em>HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·ClO<sub>4</sub>}<sup>3+</sup>·3HCOO·solvent (<strong>3</strong>·3HCOO·solvent) and {[Ni<sub>6</sub>(<em>μ</em><sub>3</sub>-OH)<sub>2</sub>(<em>μ-</em>HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·ClO<sub>4</sub>}<sup>3+</sup>·3HCOO·solvent (<strong>4</strong>·3HCOO·solvent), was constructed from shuttlecock-like <em>C</em><sub>3</sub>-symmetric [M<sub>3</sub>(<em>μ</em><sub>3</sub>-OH) (<em>μ</em>-HCOO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>] (M = Co<sup>2+</sup> or Ni<sup>2+</sup>) clusters generated in situ and a clip-like ligand 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) [pbim]. Interestingly, one SO<sub>4</sub><sup>2−</sup> or ClO<sub>4</sub><sup>−</sup> anion was encapsulated in each cage of MOCs <strong>1</strong>–<strong>4</strong> through cooperative O–H⋯O and C–H⋯O hydrogen-bonding interactions. It was also found that those SO<sub>4</sub><sup>2‒</sup>-/ClO<sub>4</sub><sup>−</sup>-encapsulated MOCs, especially SO<sub>4</sub><sup>2‒</sup>-encapsulated MOC of Ni<sup>2+</sup>, displayed quite stability in methanol. Notably, when the crystal parent solution of MOC <strong>1</strong> was disturbed or MOC <strong>1</strong> was immersed in its parent solution for a long time, it resulted in the formation of a 2D coordination polymer [Co(pbim)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·2HCOO (<strong>5</strong>) with helical architecture. Unexpectedly, a novel 2D coordination polymer [Ni<sub>4</sub>(pbim)<sub>2</sub>(CH<sub>3</sub>O)<sub>4</sub>(C<sub>6</sub>H<sub>5</sub>COO)<sub>4</sub>]·2H<sub>2</sub>O (<strong>6</strong>·2H<sub>2</sub>O) based on in-situ produced cubane-like [Ni<sub>4</sub>(<em>μ</em><sub>3</sub>-CH<sub>3</sub>O)<sub>4</sub>(<em>μ-</em>COO)<sub>2</sub>] cluster was solvothermally synthesized through the reaction of benzoic acid with relatively stable MOC <strong>2</strong> in DMF. Magnetic studies show that there are antiferromagnetic coupling exchanged by mixed hydroxyl/carboxylate bridges in shuttlecock-like [M<sub>3</sub>(<em>μ</em><sub>3</sub>-OH) (<em>μ</em>-HCOO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>] clusters of <strong>1</strong> and <strong>2</strong> or in cubane-like [Ni<sub>4</sub>(<em>μ</em><sub>3</sub>-CH<sub>3</sub>O)<sub>4</sub>(<em>μ-</em>COO)<sub>2</sub>] cluster of <strong>6</strong>. The best fits for their magnetic behaviours gave the following coupling constants: <em>J</em> = −2.05 cm<sup>−1</sup> for <strong>1</strong>, <em>J</em> = −1.74 cm<sup>−1</sup> for <strong>2</strong>, and <em>J</em><sub>1</sub> = −2.85 cm<sup>−1</sup> and <em>J</em><sub>2</sub> = −4.01 cm<sup>−1</sup> for <strong>6</strong>.</p></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hexagonal-prismatic metal‒organic cages and metal‒organic polymers based on 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) ligand: Synthesis, structural characterization and magnetic property\",\"authors\":\"\",\"doi\":\"10.1016/j.jssc.2024.124974\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A serial of hexagonal-prismatic metal organic cages (MOCs), [Co<sub>6</sub>(OH)<sub>2</sub>(HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·SO<sub>4</sub>·2HCOO·8H<sub>2</sub>O (<strong>1</strong>·2HCOO·8H<sub>2</sub>O), [Ni<sub>6</sub>(OH)<sub>2</sub>(HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·SO<sub>4</sub>·2HCOO·8H<sub>2</sub>O (<strong>2</strong>·HCOO·8H<sub>2</sub>O), {[Co<sub>6</sub>(<em>μ</em><sub>3</sub>-OH)<sub>2</sub>(<em>μ-</em>HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·ClO<sub>4</sub>}<sup>3+</sup>·3HCOO·solvent (<strong>3</strong>·3HCOO·solvent) and {[Ni<sub>6</sub>(<em>μ</em><sub>3</sub>-OH)<sub>2</sub>(<em>μ-</em>HCOO)<sub>6</sub>(pbim)<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]·ClO<sub>4</sub>}<sup>3+</sup>·3HCOO·solvent (<strong>4</strong>·3HCOO·solvent), was constructed from shuttlecock-like <em>C</em><sub>3</sub>-symmetric [M<sub>3</sub>(<em>μ</em><sub>3</sub>-OH) (<em>μ</em>-HCOO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>] (M = Co<sup>2+</sup> or Ni<sup>2+</sup>) clusters generated in situ and a clip-like ligand 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) [pbim]. Interestingly, one SO<sub>4</sub><sup>2−</sup> or ClO<sub>4</sub><sup>−</sup> anion was encapsulated in each cage of MOCs <strong>1</strong>–<strong>4</strong> through cooperative O–H⋯O and C–H⋯O hydrogen-bonding interactions. It was also found that those SO<sub>4</sub><sup>2‒</sup>-/ClO<sub>4</sub><sup>−</sup>-encapsulated MOCs, especially SO<sub>4</sub><sup>2‒</sup>-encapsulated MOC of Ni<sup>2+</sup>, displayed quite stability in methanol. Notably, when the crystal parent solution of MOC <strong>1</strong> was disturbed or MOC <strong>1</strong> was immersed in its parent solution for a long time, it resulted in the formation of a 2D coordination polymer [Co(pbim)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·2HCOO (<strong>5</strong>) with helical architecture. Unexpectedly, a novel 2D coordination polymer [Ni<sub>4</sub>(pbim)<sub>2</sub>(CH<sub>3</sub>O)<sub>4</sub>(C<sub>6</sub>H<sub>5</sub>COO)<sub>4</sub>]·2H<sub>2</sub>O (<strong>6</strong>·2H<sub>2</sub>O) based on in-situ produced cubane-like [Ni<sub>4</sub>(<em>μ</em><sub>3</sub>-CH<sub>3</sub>O)<sub>4</sub>(<em>μ-</em>COO)<sub>2</sub>] cluster was solvothermally synthesized through the reaction of benzoic acid with relatively stable MOC <strong>2</strong> in DMF. Magnetic studies show that there are antiferromagnetic coupling exchanged by mixed hydroxyl/carboxylate bridges in shuttlecock-like [M<sub>3</sub>(<em>μ</em><sub>3</sub>-OH) (<em>μ</em>-HCOO)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>] clusters of <strong>1</strong> and <strong>2</strong> or in cubane-like [Ni<sub>4</sub>(<em>μ</em><sub>3</sub>-CH<sub>3</sub>O)<sub>4</sub>(<em>μ-</em>COO)<sub>2</sub>] cluster of <strong>6</strong>. The best fits for their magnetic behaviours gave the following coupling constants: <em>J</em> = −2.05 cm<sup>−1</sup> for <strong>1</strong>, <em>J</em> = −1.74 cm<sup>−1</sup> for <strong>2</strong>, and <em>J</em><sub>1</sub> = −2.85 cm<sup>−1</sup> and <em>J</em><sub>2</sub> = −4.01 cm<sup>−1</sup> for <strong>6</strong>.</p></div>\",\"PeriodicalId\":378,\"journal\":{\"name\":\"Journal of Solid State Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-08-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Solid State Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022459624004286\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022459624004286","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Hexagonal-prismatic metal‒organic cages and metal‒organic polymers based on 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) ligand: Synthesis, structural characterization and magnetic property
A serial of hexagonal-prismatic metal organic cages (MOCs), [Co6(OH)2(HCOO)6(pbim)6(H2O)6]·SO4·2HCOO·8H2O (1·2HCOO·8H2O), [Ni6(OH)2(HCOO)6(pbim)6(H2O)6]·SO4·2HCOO·8H2O (2·HCOO·8H2O), {[Co6(μ3-OH)2(μ-HCOO)6(pbim)6(H2O)6]·ClO4}3+·3HCOO·solvent (3·3HCOO·solvent) and {[Ni6(μ3-OH)2(μ-HCOO)6(pbim)6(H2O)6]·ClO4}3+·3HCOO·solvent (4·3HCOO·solvent), was constructed from shuttlecock-like C3-symmetric [M3(μ3-OH) (μ-HCOO)3(H2O)3] (M = Co2+ or Ni2+) clusters generated in situ and a clip-like ligand 1,1'-(5-methyl-1,3-phenylene)bis(1H-imidazole) [pbim]. Interestingly, one SO42− or ClO4− anion was encapsulated in each cage of MOCs 1–4 through cooperative O–H⋯O and C–H⋯O hydrogen-bonding interactions. It was also found that those SO42‒-/ClO4−-encapsulated MOCs, especially SO42‒-encapsulated MOC of Ni2+, displayed quite stability in methanol. Notably, when the crystal parent solution of MOC 1 was disturbed or MOC 1 was immersed in its parent solution for a long time, it resulted in the formation of a 2D coordination polymer [Co(pbim)2(H2O)2]·2HCOO (5) with helical architecture. Unexpectedly, a novel 2D coordination polymer [Ni4(pbim)2(CH3O)4(C6H5COO)4]·2H2O (6·2H2O) based on in-situ produced cubane-like [Ni4(μ3-CH3O)4(μ-COO)2] cluster was solvothermally synthesized through the reaction of benzoic acid with relatively stable MOC 2 in DMF. Magnetic studies show that there are antiferromagnetic coupling exchanged by mixed hydroxyl/carboxylate bridges in shuttlecock-like [M3(μ3-OH) (μ-HCOO)3(H2O)3] clusters of 1 and 2 or in cubane-like [Ni4(μ3-CH3O)4(μ-COO)2] cluster of 6. The best fits for their magnetic behaviours gave the following coupling constants: J = −2.05 cm−1 for 1, J = −1.74 cm−1 for 2, and J1 = −2.85 cm−1 and J2 = −4.01 cm−1 for 6.
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Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.
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