Single-crystal x-ray diffraction structures of covalent organic frameworks

• Published in: Science (American Association for the Advancement of Science) Vol. 361; no. 6397; pp. 48 - 52
• Main Authors: Ma, Tianqiong, Kapustin, Eugene A., Yin, Shawn X., Liang, Lin, Zhou, Zhengyang, Niu, Jing, Li, Li-Hua, Wang, Yingying, Su, Jie, Li, Jian, Wang, Xiaoge, Wang, Wei David, Wang, Wei, Sun, Junliang, Yaghi, Omar M.
• Format: Journal Article
• Language: English
• Published: United States The American Association for the Advancement of Science 06.07.2018
• Subjects: Absorption spectroscopy; Amorphous materials; Aniline; Charge transport; Covalence; Crystal structure; Crystallites; Crystallization; Crystals; Diffraction; Electron diffraction; Literary Devices; Nanoparticles; Nucleation; Organic chemistry; Powder; Seeds; Single crystals; Structural analysis; Topology; X-ray diffraction
• ISSN: 0036-8075; 1095-9203; 1095-9203
• DOI: 10.1126/science.aat7679

Covalent organic framework (COF) materials have been difficult to characterize structurally and to exploit because they tend to form powders or amorphous materials. Ma et al. studied a variety of three-dimensional COFs based on imine linkages (see the Perspective by Navarro). They found that the addition of aniline inhibited nucleation and allowed the growth of crystals large enough for single-crystal x-ray diffraction studies. Evans et al. describe a two-step process in which nanoscale seeds of boronate ester–linked two-dimensional COFs can be grown into micrometer-scale single crystals by using a solvent that suppresses the nucleation of additional nanoparticles. Transient absorption spectroscopy revealed superior charge transport in these crystallites compared with that observed in conventional powders. Science , this issue p. 48 , p. 52 ; see also p. 35 The addition of aniline enables the growth of single crystals of imine-based covalent organic framework materials. The crystallization problem is an outstanding challenge in the chemistry of porous covalent organic frameworks (COFs). Their structural characterization has been limited to modeling and solutions based on powder x-ray or electron diffraction data. Single crystals of COFs amenable to x-ray diffraction characterization have not been reported. Here, we developed a general procedure to grow large single crystals of three-dimensional imine-based COFs (COF-300, hydrated form of COF-300, COF-303, LZU-79, and LZU-111). The high quality of the crystals allowed collection of single-crystal x-ray diffraction data of up to 0.83-angstrom resolution, leading to unambiguous solution and precise anisotropic refinement. Characteristics such as degree of interpenetration, arrangement of water guests, the reversed imine connectivity, linker disorder, and uncommon topology were deciphered with atomic precision—aspects impossible to determine without single crystals.