低价金属离子作为 MOF 支柱：通往稳定和多功能 MOF 的新途径,Journal of the American Chemical Society

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低价金属离子作为 MOF 支柱：通往稳定和多功能 MOF 的新途径
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-08-19 , DOI: 10.1021/jacs.1c05564
R Eric Sikma ₁ , Naman Katyal ₁ , Su-Kyung Lee ₂ , Joseph W Fryer ₃ , Catherine G Romero ₃ , Samuel K Emslie _{1,

3} , Elinor L Taylor ₃ , Vincent M Lynch ₁ , Jong-San Chang ₂ , Graeme Henkelman ₁ , Simon M Humphrey ₁

Affiliation

PCM-102 是一种新型有机膦金属-有机骨架（MOF），具有由成对的偏移反式P(III) 供体组成的二膦袋。将 M(I) 盐（M = Cu、Ag、Au）合成后添加到 PCM-102 会诱导单晶到单晶的转变和反式-[P ₂ M] ⁺固态复合物的形成（其中 P =基于骨架的三芳基膦）。虽然非金属化 PCM-102 的孔隙率较低，但添加二级路易斯酸以安装刚性 P-M-P 柱显示出显着提高稳定性和选择性气体吸收性能，N ₂ Brunauer-Emmett-Teller 表面积 >1500米²克^–1. Ag(I) 类似物也可以通过简单的一锅围合成路线获得，并且是通过合成后溶剂辅助金属交换混合双金属 M ^A / M ^B柱的材料的理想牺牲前体。值得注意的是，M-PCM-102 系列 MOF 包含周期性反式-[P ₂ M] ⁺与传统的类似分子复合物不同，不含抗衡阴离子的位点，因为前体 PCM-102 MOF 是单阴离子的，能够获得电荷中性的金属柱撑材料。对四种 M-PCM-102 材料的 C2 烃分离进行了评估。发现分离性能可根据所掺入的金属进行调节，并且采用密度泛函理论来阐明异常观察到的吸附偏好的性质，C ₂ H ₂ > C ₂ H ₆ > C ₂ H ₄。

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Low-Valent Metal Ions as MOF Pillars: A New Route Toward Stable and Multifunctional MOFs

PCM-102 is a new organophosphine metal–organic framework (MOF) featuring diphosphine pockets that consist of pairs of offset trans-oriented P(III) donors. Postsynthetic addition of M(I) salts (M = Cu, Ag, Au) to PCM-102 induces single-crystal to single-crystal transformations and the formation of trans-[P₂M]⁺ solid-state complexes (where P = framework-based triarylphosphines). While the unmetalated PCM-102 has low porosity, the addition of secondary Lewis acids to install rigid P–M–P pillars is shown to dramatically increase both stability and selective gas uptake properties, with N₂ Brunauer–Emmett–Teller surface areas >1500 m² g^–1. The Ag(I) analogue can also be obtained via a simple, one-pot peri-synthetic route and is an ideal sacrificial precursor for materials with mixed bimetallic M^A/M^B pillars via postsynthetic, solvent-assisted metal exchange. Notably, the M-PCM-102 family of MOFs contain periodic trans-[P₂M]⁺ sites that are free of counter anions, unlike traditional analogous molecular complexes, since the precursor PCM-102 MOF is monoanionic, enabling access to charge-neutral metal-pillared materials. Four M-PCM-102 materials were evaluated for the separation of C2 hydrocarbons. The separation performance was found to be tunable based on the metal(s) incorporated, and density functional theory was employed to elucidate the nature of the unusual observed sorption preference, C₂H₂ > C₂H₆ > C₂H₄.

更新日期：2021-09-01

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