{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T10:28:28Z","timestamp":1787048908479,"version":"build-2736575974"},"reference-count":45,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T00:00:00Z","timestamp":1787011200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T00:00:00Z","timestamp":1787011200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Anisotropic thermal expansion in molecular crystals has predominantly been reported for low\u2010\n                    <jats:italic>Z<\/jats:italic>\n                    \u2032 systems (\n                    <jats:italic>Z<\/jats:italic>\n                    \u2032 \u2264 2), in which only a few independent molecules occupy the asymmetric unit. In such crystals, thermal expansion is often interpreted using simplified models based on rigid molecular motion or averaged intermolecular interactions. However, these descriptions fail to capture the complex anisotropy, switchable responses, and multistep phase transitions frequently observed in molecular solids. Here, we report high\u2010\n                    <jats:italic>Z<\/jats:italic>\n                    \u2032 molecular crystals that exhibit both thermal robustness and stepwise, rapid anisotropic thermal expansion upon temperature variation. These crystals were designed by combining substituent\u2010induced molecular asymmetry, competitive intermolecular interactions, and flexible intramolecular degrees of freedom. Crystals of 2,6\u2010bis(4\u2010\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butylphenyl)anthracene display an unusually high\n                    <jats:italic>Z<\/jats:italic>\n                    \u2032 value of 5 over a wide temperature range (100\u2013400 K), enabled by the noncovalent immobilization of coplanar\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl groups within a herringbone packing framework. Upon heating, progressive molecular motions induce dynamic averaging of crystallographically distinct local environments, culminating in a cooperative phase transition accompanied by symmetry recovery and reduction of\n                    <jats:italic>Z<\/jats:italic>\n                    ' from 5 to 2.5 at 423 K. The resulting structural reorganization gives rise to rapid macroscopic anisotropic thermal expansion. These results establish high\u2010\n                    <jats:italic>Z<\/jats:italic>\n                    \u2032 crystal engineering as a viable strategy for programmable and reversible thermal\u2010mechanical responses.\n                  <\/jats:p>","DOI":"10.1002\/smll.75273","type":"journal-article","created":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T09:56:52Z","timestamp":1787047012000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["From Simplicity to Complexity: Substituent\u2010Controlled\n                    <i>Z<\/i>\n                    \u2032 Multiplicity as a Design Principle for Thermally Robust Yet Programmable Anisotropic Expansion"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3170-2959","authenticated-orcid":false,"given":"Yuto","family":"Hino","sequence":"first","affiliation":[{"name":"School of Engineering Science Kochi University of Technology  Kami Kochi Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0874-4798","authenticated-orcid":false,"given":"Takumi","family":"Matsuo","sequence":"additional","affiliation":[{"name":"School of Engineering Science Kochi University of Technology  Kami Kochi Japan"},{"name":"FOREST Center Research Institute Kochi University of Technology  Kami Kochi Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tomohiro","family":"Yamashita","sequence":"additional","affiliation":[{"name":"School of Materials and Chemical Technology Institute of Science Tokyo  Yokohama Kanagawa Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2191-9257","authenticated-orcid":false,"given":"Hiroko","family":"Yokota","sequence":"additional","affiliation":[{"name":"School of Materials and Chemical Technology Institute of Science Tokyo  Yokohama Kanagawa 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