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Framework Isomerism in Vanadium Metal–Organic Frameworks: MIL-88B(V) and MIL-101(V)

DOI: 10.1021/cg4012058 DOI Help

Authors: Fabian Carson (Stockholm University) , Jie Su , Ana Platero-Prats (Stockholm University) , Wei Wan , Yifeng Yun , Louise Samain , Xiaodong Zou (Structural Chemistry, Stockholm University, SE-10691 Stockholm, Sweden)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Crystal Growth & Design , VOL 13 (11)

State: Published (Approved)
Published: October 2013

Abstract: Two families of metal–organic frameworks (MOFs), MIL-88 and MIL-101 built by trinuclear transition metal (TM) clusters (TM = Cr, Fe, or Sc), have been known for several years, but their syntheses are often reported separately. In fact, these MOFs are polymorphs, or framework isomers: they are assembled from the same metal secondary building units and organic linkers, but the connectivity of these components differs. Here we report for the first time the synthesis of the vanadium MOF MIL-88B(V) and compare its synthesis parameters to those of MIL-47(V) and the recently reported MIL-101(V). The properties of MIL-88B(V) and MIL-101(V) are remarkably different. MIL-88B(V) can “breathe” and is responsive to different solvents, while MIL-101(V) is rigid and contains mesoporous cages. MIL-101(V) exhibits the highest specific surface area among vanadium MOFs discovered so far. In addition, both MIL-88B(V) and MIL-101(V) transform to MIL-47 at higher temperatures. We have also identified the key synthesis parameters that control the formation of MIL-88B(V), MIL-101(V), and MIL-47: temperature, time, and pH. This relates to the rate of reaction between the metal and linkers, which has been monitored by ex situ X-ray powder diffraction and V K-edge X-ray absorption spectroscopy during MOF synthesis. It is therefore important to fully study the synthesis conditions to improve our understanding of framework isomerism in MOFs.

Journal Keywords: Framework Isomerism In Vanadium Metal–Organic Frameworks: Mil-88B(V) And Mil-101(V)

Subject Areas: Materials, Chemistry

Instruments: I11-High Resolution Powder Diffraction

Other Facilities: beamline I811, MAX-lab, Sweden