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This work demonstrates that dynamic structural disorder can play a central role in governing proton dynamics, even in essentially non\u2010porous systems. We report the synthesis and comparative analysis of three positional isomers of pyridinediyldiphosphonic acid 2,6\u2010, 2,5\u2010, and 3,5\u2010 \u2013 providing a systematic platform for investigating structure\u2013property relationships. Among them, the 2,5\u2010isomer exhibits an outstanding proton conductivity of \u00a0S\u00a0 at room temperature and 97% relative humidity, despite its essentially non\u2010porous nature (BET \u00a0\u00a0). A humidity\u2010driven decrease in activation energy from 0.46 to 0.15\u00a0eV reveals a transition from vehicle\u2010assisted transport to a Grotthuss\u2010type proton\u2010hopping mechanism. Crystallographic analysis demonstrates pronounced positional and dynamic disorder, while ATR\u2013FTIR spectroscopy reveals a Zundel\u2010type continuum indicative of highly polarized and delocalized protons. We show that structural disorder enables adaptive reorganization of hydrogen\u2010bond networks upon hydration, generating efficient proton\u2010conduction pathways without permanent pores. These findings challenge the prevailing paradigm that permanent porosity is essential for proton\u2010conducting HOFs and establish dynamic disorder as a powerful design principle for solid\u2010state proton\u00a0conductors.<\/jats:p>","DOI":"10.1002\/smll.75935","type":"journal-article","created":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T14:47:37Z","timestamp":1790347657000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Functional Structural Disorder Governing Efficient Proton Transport in Non\u2010Porous Phosphonic\u2010Acid\u2010Based HOFs"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-8789-4855","authenticated-orcid":false,"given":"Patrycja","family":"K\u0105dzia\u0142ka","sequence":"first","affiliation":[{"name":"Department of Physical and Quantum Chemistry Faculty of Chemistry Wroc\u0142aw University of Science and Technology  Wroc\u0142aw Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3474-5302","authenticated-orcid":false,"given":"Krzysztof","family":"Kierzek","sequence":"additional","affiliation":[{"name":"Department of Process Engineering and Technology of Polymer and Carbon Materials Faculty of Chemistry Wroc\u0142aw University of Science and Technology  Wroc\u0142aw Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1593-2719","authenticated-orcid":false,"given":"B\u0142a\u017cej","family":"Dziuk","sequence":"additional","affiliation":[{"name":"Institute of Advanced Materials Faculty of Chemistry Wroc\u0142aw University of Science and Technology  Wroc\u0142aw Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8243-9313","authenticated-orcid":false,"given":"Tomasz K.","family":"Olszewski","sequence":"additional","affiliation":[{"name":"Department of Physical and Quantum Chemistry Faculty of Chemistry Wroc\u0142aw University of Science and Technology  Wroc\u0142aw Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6595-7896","authenticated-orcid":false,"given":"Tomasz","family":"Misiaszek","sequence":"additional","affiliation":[{"name":"Department of Physical and Quantum Chemistry Faculty of Chemistry Wroc\u0142aw University of Science and Technology  Wroc\u0142aw Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,25]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.rser.2014.01.012"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/d0cs00296h"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ACSENERGYLETT.1C02045\/ASSET\/IMAGES\/LARGE\/NZ1C02045_0009.JPEG"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/ADFM.202409359"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC07802A"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC02628D"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/natrevmats.2015.18"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/ANIE.201804753"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1126\/SCIADV.ADW5747\/SUPPL_FILE\/SCIADV.ADW5747_SM.PDF"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/ADFM.202210036"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ACSCENTSCI.9B00750"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ACSCENTSCI.0C00592"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ADFM.202515358"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ACSNANO.6C05987"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/ADFM.202520568"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/JA963905E\/SUPPL_FILE\/JA2737.PDF"},{"issue":"12","key":"e_1_2_8_18_1","doi-asserted-by":"crossref","first-page":"4696","DOI":"10.1021\/ja00012a057","article-title":"Use of Hydrogen Bonds to Control Molecular Aggregation. 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