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

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Journal of Solid State Chemistry Pub Date : 2024-08-28 DOI:10.1016/j.jssc.2024.124974

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Abstract

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 SO₄^2‒-/ClO₄⁻-encapsulated MOCs, especially SO₄^2‒-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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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

一系列六方棱柱形金属有机笼（MOC），[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 溶剂（3-3HCOO 溶剂）和{[Ni6(μ3-OH)2(μ-HCOO)6(pbim)6(H2O)6]-ClO4}3+-3HCOO 溶剂（4-3HCOO 溶剂）、是由原位生成的梭形 C3 对称[M3(μ3-OH) (μ-HCOO)3(H2O)3] (M = Co2+ 或 Ni2+)团簇和夹子状配体 1,1'-(5-甲基-1,3-亚苯基)双(1H-咪唑) [pbim]构建而成。有趣的是，通过 O-H⋯O 和 C-H⋯O 氢键相互作用，一个 SO42- 或 ClO4- 阴离子被包裹在 MOCs 1-4 的每个笼中。研究还发现，SO42--/ClO4--包裹的MOC，尤其是SO42--包裹的Ni2+ MOC，在甲醇中表现出相当高的稳定性。值得注意的是，当 MOC 1 的晶体母液受到干扰或 MOC 1 长期浸泡在母液中时，会形成具有螺旋结构的二维配位聚合物 [Co(pbim)2(H2O)2]-2HCOO（5）。意想不到的是，通过苯甲酸与相对稳定的 MOC 2 在 DMF 中的反应，在原位生成的立方体状 [Ni4(μ3-CH3O)4(μ-COO)2]簇的基础上，溶解热合成了一种新型二维配位聚合物 [Ni4(pbim)2(CH3O)4(C6H5COO)4]-2H2O（6-2H2O）。磁学研究表明，在 1 和 2 的梭子蟹状 [M3(μ3-OH) (μ-HCOO)3(H2O)3] 簇或 6 的立方体状 [Ni4(μ3-CH3O)4(μ-COO)2]簇中存在由羟基/羧酸盐混合桥交换的反铁磁耦合：1 的 J = -2.05 cm-1，2 的 J = -1.74 cm-1，6 的 J1 = -2.85 cm-1 和 J2 = -4.01 cm-1。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： 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.