Li, XiaolinWang, JuehuaBai, NannanZhang, Xinran; orcid: 0000-0002-0734-6173Han, Xueda Silva, Ivan; orcid: 0000-0002-4472-9675Morris, Christopher G.Xu, Shaojun; orcid: 0000-0002-8026-8714Wilary, Damian M.Sun, Yinyong; orcid: 0000-0002-5570-5089Cheng, YongqiangMurray, Claire A.Tang, Chiu C.Frogley, Mark D.; orcid: 0000-0002-0742-5007Cinque, GianfeliceLowe, TristanZhang, HaifeiRamirez-Cuesta, Anibal J.; orcid: 0000-0003-1231-0068Thomas, K. Mark; orcid: 0000-0002-8661-3099Bolton, Leslie W.Yang, Sihai; orcid: 0000-0002-1111-9272; email: Sihai.Yang@manchester.ac.ukSchröder, Martin; orcid: 0000-0001-6992-0700; email: m.schroder@manchester.ac.uk2021-08-272021-08-272020-08-272019-07-23Nature Communications, volume 11, issue 1, page 4280http://hdl.handle.net/10034/625710From Springer Nature via Jisc Publications RouterHistory: received 2019-07-23, accepted 2020-07-06, registration 2020-07-14, pub-electronic 2020-08-27, online 2020-08-27, collection 2020-12Publication status: PublishedFunder: RCUK | Engineering and Physical Sciences Research Council (EPSRC); doi: https://doi.org/10.13039/501100000266; Grant(s): EP/I011870Funder: EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council); doi: https://doi.org/10.13039/100010663; Grant(s): 742401Abstract: The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes.Licence for this article: http://creativecommons.org/licenses/by/4.0/Article/639/638/298/921/639/301/299/921/145/128articlearticle2021-08-27