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A common approach for separations is to crystallize a host molecule that either provides an enforced covalent cavity (intrinsic cavity) or packs inefficiently (extrinsic cavity). Here we report a self-assembled molecule with a shape highly biased to completely enclose space and, thereby, pack efficiently yet hosts and allows for the separation of BTEX hydrocarbons (i.e., benzene, toluene, ethylbenzene, xylenes). The host is held together by N\u2009\u2192\u2009B bonds and forms a diboron assembly with a shape that conforms to a T-shaped pentomino. A T-pentomino is a polyomino, which is a plane figure that tiles a plane without cavities and holes, and we show the molecule to crystallize into one of six polymorphic structures for T-pentomino tiling. The separations occur at mild conditions while rejecting similarly shaped aromatics such as xylene isomers, thiophene, and styrene. Our observation on the structure and tiling of the molecular T-pentomino allows us to develop a theory on how novel synthetic molecules that mimic the structures and packing of polyominoes can be synthesized and\u2014quite counterintuitively\u2014developed into a system of hosts with cavities used for selective and useful separations.<\/jats:p>","DOI":"10.1038\/s41467-024-45542-2","type":"journal-article","created":{"date-parts":[[2024,3,8]],"date-time":"2024-03-08T03:02:05Z","timestamp":1709866925000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["A molecular T-pentomino for separating BTEX hydrocarbons"],"prefix":"10.1038","volume":"15","author":[{"given":"Christopher J.","family":"Hartwick","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eric W.","family":"Reinheimer","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0875-677X","authenticated-orcid":false,"given":"Leonard R.","family":"MacGillivray","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2024,3,8]]},"reference":[{"key":"45542_CR1","doi-asserted-by":"publisher","first-page":"435","DOI":"10.1038\/532435a","volume":"532","author":"DS Sholl","year":"2016","unstructured":"Sholl, D. 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Nature 389, 469\u2013472 (1997).","journal-title":"Nature"},{"key":"45542_CR5","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-019-12453-6","volume":"10","author":"Y Li","year":"2019","unstructured":"Li, Y. et al. Hydrogen-bonded frameworks for molecular structure determination. Nat. Commun. 10, 4477 (2019).","journal-title":"Nat. Commun."},{"key":"45542_CR6","doi-asserted-by":"crossref","unstructured":"Hartwick, C. J. et al. Self-Assembly of Diboronic Esters with U-Shaped Bipyridines: \"Plug-in-Socket\" Assemblies. Cryst. Growth Des. 21, 4482\u20134487 (2021).","DOI":"10.1021\/acs.cgd.1c00382"},{"key":"45542_CR7","doi-asserted-by":"crossref","unstructured":"Ghosn, M. W. & Wolf, C. Stereocontrolled photodimerization with congested 1,8-bis(4'-anilino)naphthalene templates. J. Org. Chem. 75, 6653\u20136659 (2010).","DOI":"10.1021\/jo101547w"},{"key":"45542_CR8","doi-asserted-by":"crossref","unstructured":"Vargas-Olvera, E. C. et al. Molecular dynamics studies of aromatic guests in three isostructural inclusion compounds with molecular boron\u2013nitrogen hosts. Cryst. Growth Des. 22, 570\u2013584 (2021).","DOI":"10.1021\/acs.cgd.1c01140"},{"key":"45542_CR9","doi-asserted-by":"publisher","first-page":"5108","DOI":"10.1021\/acs.cgd.0c00288","volume":"20","author":"AD Herrera-Espa\u00f1a","year":"2020","unstructured":"Herrera-Espa\u00f1a, A. D., Montes-Tolentino, P., Dom\u00ednguez-Ch\u00e1vez, J. G., H\u00f6pfl, H. & Morales-Rojas, H. Crystal-to-cocrystal transformation as a novel approach for the removal of aromatic sulfur compounds from fuels. Cryst. Growth Des. 20, 5108\u20135119 (2020).","journal-title":"Cryst. Growth Des."},{"key":"45542_CR10","unstructured":"Gr\u00fcnbaum, B. & Shephard, G. C. Tilings and Patterns, 2nd edn (Dover Books on Mathematics) Illustrated Edition. (W. H. 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