title: Principles of Designing Extra-Large Pore Openings and Cages in Zeolitic Imidazolate Frameworks.
abstract: We report three design principles for obtaining extra-large pore openings and cages in the metal-organic analogues of inorganic zeolites, zeolitic imidazolate frameworks (ZIFs). Accordingly, we prepared a series of 15 ZIFs, members of which have the largest pore opening (22.5 Å) and the largest cage size (45.8 Å) known for all porous tetrahedral structures. The key parameter allowing us to access these exceptional ZIFs is what we define as the steric index (δ), which is related to the size and shape of the imidazolate linkers employed in the synthesis. The three principles are based on using multiple linkers with specific range and ratios of δ to control the size of rings and cages from small to large, and therefore are universally applicable to all existing ZIFs. The ZIF with the largest cage size (ZIF-412) shows the best selectivity of porous materials tested toward removal of octane and p-xylene from humid air.
authors.affiliation: Department of Chemistry, University of California, Berkeley , Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States.
authors.forename: Jingjing
authors.identifier: 0000-0002-1192-7368
authors.initials: J
authors.lastname: Yang
authors.affiliation: Department of Chemistry, University of California, Berkeley , Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States.
authors.forename: Yue-Biao
authors.identifier: 0000-0002-8270-1067
authors.initials: YB
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, China.|UC Berkeley, Global Science Institute - Wuhan University, the Insitute of Advanced Studies Joint Innovative Center, Wuhan University , Wuhan 430072, China.
authors.forename: Qi
authors.initials: Q
authors.lastname: Liu
authors.affiliation: Department of Chemistry, University of California, Berkeley , Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States.
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Trickett
authors.affiliation: Instituto de Ciencia de Materiales de Madrid-CSIC , Sor Juana Inés de la Cruz 3, 20849 Madrid, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Gutiérrez-Puebla
authors.affiliation: Instituto de Ciencia de Materiales de Madrid-CSIC , Sor Juana Inés de la Cruz 3, 20849 Madrid, Spain.
authors.forename: M Ángeles
authors.initials: MÁ
authors.lastname: Monge
authors.affiliation: Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, China.
authors.forename: Hengjiang
authors.initials: H
authors.lastname: Cong
authors.affiliation: Department of Chemistry, University of California, Berkeley , Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States.
authors.forename: Abdulrahman
authors.initials: A
authors.lastname: Aldossary
authors.affiliation: Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, China.|UC Berkeley, Global Science Institute - Wuhan University, the Insitute of Advanced Studies Joint Innovative Center, Wuhan University , Wuhan 430072, China.
authors.forename: Hexiang
authors.initials: H
authors.lastname: Deng
authors.affiliation: Department of Chemistry, University of California, Berkeley , Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States.|UC Berkeley, Global Science Institute - Wuhan University, the Insitute of Advanced Studies Joint Innovative Center, Wuhan University , Wuhan 430072, China.|King Abdulaziz City for Science and Technology , Riyadh 11442, Saudi Arabia.
authors.forename: Omar M
authors.identifier: 0000-0002-5611-3325
authors.initials: OM
authors.lastname: Yaghi
mesh_terms: D007093:Imidazoles / Q000737:chemistry*; D000073396:Metal-Organic Frameworks / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D017641:Zeolites / Q000737:chemistry*
chemical_list: D007093:Imidazoles; D000073396:Metal-Organic Frameworks; D017641:Zeolites