Role of a Modulator in the Synthesis of Phase-Pure NU-1000

• Published in: ACS applied materials & interfaces Vol. 9; no. 45; pp. 39342 - 39346
• Main Authors: Webber, Thomas E., Liu, Wei-Guang, Desai, Sai Puneet, Lu, Connie C., Truhlar, Donald G., Penn, R. Lee
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.11.2017; American Chemical Society (ACS)
• Subjects: benzoic acid; catalysis (heterogeneous); coordination polymers; crystals; dimethylformamide; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; materials and chemistry by design; porous media; synthesis (novel materials); temperature; metal infiltration; phase-pure synthesis; modulator; metal−organic frameworks; NU-1000
• ISSN: 1944-8244; 1944-8252; 1944-8252
• DOI: 10.1021/acsami.7b11348

NU-1000 is a robust, mesoporous metal–organic framework (MOF) with hexazirconium nodes ([Zr6O16H16]8+, referred to as oxo–Zr6 nodes) that can be synthesized by combining a solution of ZrOCl2·8H2O and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis­(p-benzoic acid)­pyrene, referred to as H4TBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo–Zr6 nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo–Zr6 node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurally heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.