Unravelling Crystal Structures of Covalent Organi Frameworks by Electron Diffraction Tomography

Featuring the art of covalent chemistry on 2D and 3D with molecular precision,covalent organic frameworks(COFs)have attracted immense interests from inorganic,organic,polymer,materials and energy chemistry.However,due to the synthetic challenge of"crystallization problem",structural determination of COFs has been the bottle-neck in speeding up their discovery and design,as well as building up their structureproperty relation.Electron diffraction tomography(EDT)has been developed to determine crystal structures of COFs with only sub-micrometer sized single crystals,which enabled the ob initio determination of crystal structure,molecular connectivity,pore metrics,and host-guest interaction at the atomic level.In this review,w e summarized the recent developments of EDT for addressing challenges in structure determinations of such e-beam sensitive,organic porous crystals,covering comprehensively automatic data collection,low dose,cryogenic protocols,structural solution method,powder X-ray diffraction refinement,and high-resolution transmission electron microscopy(HRTEM)imaging techniques.We do believe the EDT will propel this field into the new era of COF chemistry with atomic precision,and we envision the wide application of artificial intelligence will promote the structural determination and particle analysis of COFs and related materials。