1193093-31-0Relevant articles and documents
Post-synthetic reversible incorporation of organic linkers into porous metal-organic frameworks through single-crystal-to-single-crystal transformations and modification of gas-sorption properties
Park, Hye Jeong,Cheon, Young Eun,Suh, Myunghyun Paik
, p. 11662 - 11669 (2010)
The porous metal-organic framework (MOF) {[Zn2(TCPBDA)-(H 2O)2]·30DMF·6H2O}n (SNU-30; DMF=N,N-dimethylformamide) has been prepared by the solvothermal reaction of N,N,N′,N′-tetrakis(4-carboxyphenyl)biphenyl-4,4′- diamine (H4TCPBDA) and Zn(NO3)2·6H 2O in DMF/tBuOH. The post-synthetic modification of SNU-30 by the insertion of 3,6-di(4-pyridyl)-1,2,4,5-tetrazine (bpta) affords single-crystalline {[Zn2-(TCPBDA)(bpta)]·23DMF·4H 2O}n (SNU-31SC), in which channels are divided by the bpta linkers. Interestingly, unlike its pristine form, the bridging bpta ligand in the MOF is bent due to steric constraints. SNU-31 can be also prepared through a one-pot solvothermal synthesis from ZnII, TCPBDA4-, and bpta. The bpta linker can be liberated from this MOF by immersion in N,N-diethylformamide (DEF) to afford the single-crystalline SNU-30 SC, which is structurally similar to SNU-30. This phenomenon of reversible insertion and removal of the bridging ligand while preserving the single crystallinity is unprecedented in MOFs. Desolvated solid SNU-30' adsorbs N2, O 2, H2, CO2, and CH4 gases, whereas desolvated SNU-31' exhibits selective adsorption of CO2 over N 2, O2, H2, and CH4, thus demonstrating that the gas adsorption properties of MOF can be modified by post-synthetic insertion/removal of a bridging ligand.
