title: In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework.
abstract: Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.
authors: Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec, Canada H3A 0B8.
authors: Athanassios D
authors: AD
authors: Katsenis
authors: Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, HR-10000, Croatia.
authors: Andreas
authors: A
authors: Puškarić
authors: 1] Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec, Canada H3A 0B8 [2] Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, HR-10000, Croatia.
authors: Vjekoslav
authors: V
authors: Štrukil
authors: Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec, Canada H3A 0B8.
authors: Cristina
authors: C
authors: Mottillo
authors: Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec, Canada H3A 0B8.
authors: Patrick A
authors: PA
authors: Julien
authors: Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, HR-10000, Croatia.
authors: Krunoslav
authors: K
authors: Užarević
authors: Department of Chemical Engineering, Université Laval, Quebec City, Québec, Canada G1V 0A6.
authors: Minh-Hao
authors: MH
authors: Pham
authors: Department of Chemical Engineering, Université Laval, Quebec City, Québec, Canada G1V 0A6.
authors: Trong-On
authors: TO
authors: Do
authors: ESRF-The European Synchrotron, CS 40220, Grenoble 38043, France.
authors: Simon A J
authors: SA
authors: Kimber
authors: Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, HR-10000, Croatia.
authors: Predrag
authors: P
authors: Lazić
authors: Scientific Service Group X-ray Diffraction, Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany.
authors: Oxana
authors: O
authors: Magdysyuk
authors: Scientific Service Group X-ray Diffraction, Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany.
authors: Robert E
authors: RE
authors: Dinnebier
authors: Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, HR-10000, Croatia.
authors: Ivan
authors: I
authors: Halasz
authors: Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Québec, Canada H3A 0B8.
authors: Tomislav
authors: T
authors: Friščić