title: Geometry analysis and systematic synthesis of highly porous isoreticular frameworks with a unique topology.
abstract: Porous coordination polymers are well known for their easily tailored framework structures and corresponding properties. Although systematic modulations of pore sizes of binary prototypes have gained great success, simultaneous adjustment of both pore size and shape of ternary prototypes remains unexplored, owing to the difficulty in controlling the self-assembly of multiple molecular building blocks. Here we show that simple geometry analysis can be used to estimate the influence of the linker lengths and length ratios on the synthesis/construction difficulties and framework stabilities of a highly symmetric, ternary prototype composed of a typical trinuclear metal cluster and two types of bridging carboxylate ligands. As predicted, systematic syntheses with 5×5 ligand combinations produced 13 highly porous isoreticular frameworks, which show not only systematic adjustment of pore volumes (0.49-2.04 cm(3) g(-1)) and sizes (7.8-13.0 Å; 5.2-12.0 Å; 7.4-17.4 Å), but also anisotropic modulation of the pore shapes.
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, PR China.
authors.forename: Yue-Biao
authors.initials: YB
authors.lastname: Zhang
authors.forename: Hao-Long
authors.initials: HL
authors.lastname: Zhou
authors.forename: Rui-Biao
authors.initials: RB
authors.lastname: Lin
authors.forename: Chi
authors.initials: C
authors.lastname: Zhang
authors.forename: Jian-Bin
authors.initials: JB
authors.lastname: Lin
authors.forename: Jie-Peng
authors.initials: JP
authors.lastname: Zhang
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Chen
mesh_terms: D000042:Absorption; D002264:Carboxylic Acids / Q000737:chemistry; D018360:Crystallography, X-Ray / Q000379:methods; D007700:Kinetics; D008024:Ligands; D008422:Materials Testing; D008962:Models, Theoretical; D008968:Molecular Conformation; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D016062:Porosity; D013696:Temperature
chemical_list: D002264:Carboxylic Acids; D008024:Ligands; D011108:Polymers