Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic build...Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.展开更多
基金supported by the National Natural Science Foundation of China(22101047,92261109,22371280)the Natural Science Foundation of Fujian Province(2023J01219)+5 种基金the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2023-JQ06,CXZX-2022-JQ11)the XMIREM Autonomously Deployment Project(2023GG02,2023CX04)the FJIRSM Autonomously Deployment Project(CXZX-2022-GH02)the Project Funded by China Postdoctoral Science Foundation(2023M733496)the Recruitment Program of Global Youth Expertsthe Youth Innovation Promotion Association CAS(2021302)。
文摘Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.
