title: Topology-guided design and syntheses of highly stable mesoporous porphyrinic zirconium metal-organic frameworks with high surface area.
abstract: Through a topology-guided strategy, a series of Zr6-containing isoreticular porphyrinic metal-organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr8 cluster with a smaller Zr6 cluster in a topologically identical framework. The high connectivity of the Zr6 cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77842-3012, United States.
authors.forename: Tian-Fu
authors.initials: TF
authors.lastname: Liu
authors.forename: Dawei
authors.initials: D
authors.lastname: Feng
authors.forename: Ying-Pin
authors.initials: YP
authors.lastname: Chen
authors.forename: Lanfang
authors.initials: L
authors.lastname: Zou
authors.forename: Mathieu
authors.initials: M
authors.lastname: Bosch
authors.forename: Shuai
authors.initials: S
authors.lastname: Yuan
authors.forename: Zhangwen
authors.initials: Z
authors.lastname: Wei
authors.forename: Stephen
authors.initials: S
authors.lastname: Fordham
authors.forename: Kecheng
authors.initials: K
authors.lastname: Wang
authors.forename: Hong-Cai
authors.initials: HC
authors.lastname: Zhou
mesh_terms: D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010316:Particle Size; D016062:Porosity; D013499:Surface Properties; D015040:Zirconium / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D015040:Zirconium