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Here we report the first host\u2013guest chemistry of ARP. In water, hydrophobic ARP threads through\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010 or\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010cyclodextrin (CD) to produce water\u2010soluble pseudo\u2010polyrotaxanes, as evidenced by nuclear magnetic resonance (NMR) spectroscopy, atomic force microscopy (AFM) imaging and AFM\u2010based single\u2010molecule force spectroscopy (SMFS).\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010CD, whose cavity diameter (0.60 nm) matches the 0.582 nm van\u2010der\u2010Waals width of ARP, assembles readily with ARP;\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010CD, which has a smaller cavity, requires conformational distortion before assembly, producing only \u223c30% fully threaded chains even after 10 days. Threading converts collapsed ARP globules into extended chains whose mechanical stiffness increases with CD coverage. After assembly with\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010CD, the water solubility of ARP can be significantly enhanced, which builds a method to tune the hydrophilicity of an inorganic polymer chain without the need for traditional chemical modification. This work establishes ARP as an inorganic building block for supramolecular assembly, opening routes to phosphorus\u2010based functional materials.\n                  <\/jats:p>","DOI":"10.1002\/smll.202512805","type":"journal-article","created":{"date-parts":[[2026,1,17]],"date-time":"2026-01-17T09:50:01Z","timestamp":1768643401000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Amorphous Red Phosphorus: Host\u2013Guest Assembly with Cyclodextrin"],"prefix":"10.1002","volume":"22","author":[{"given":"Jiulong","family":"Zhou","sequence":"first","affiliation":[{"name":"Key Laboratory of Advanced Technologies of Materials (Ministry of Education) Southwest Jiaotong University  Chengdu China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lifeng","family":"Yao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Advanced Technologies of Materials (Ministry of Education) Southwest 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