{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T13:14:00Z","timestamp":1788354840125,"version":"build-2803163510"},"reference-count":65,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2026,5,7]],"date-time":"2026-05-07T00:00:00Z","timestamp":1778112000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,5,7]],"date-time":"2026-05-07T00:00:00Z","timestamp":1778112000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["NSF\u2010MSN\u2010CHE 2404168"],"award-info":[{"award-number":["NSF\u2010MSN\u2010CHE 2404168"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small Methods"],"published-print":{"date-parts":[[2026,6]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    On\u2010surface reactions within self\u2010assembled molecular networks offer a powerful strategy for nanoscale interface design, but must balance molecular layer stability with the local dynamics required for bond formation. Here, we develop a framework for identifying optimal reaction conditions in the topochemical polymerization of diacetylene monolayers on 2D materials. By systematically varying H\u2010bonding headgroup chemistry (COOH, OH, and NH\n                    <jats:sub>2<\/jats:sub>\n                    ), we examine how bulk and surface\u2010confined structural transitions can be used to establish a window of optimal on\u2010surface polymerization efficiency. Combining temperature\u2010dependent polymerization measurements with atomic force microscopy, differential scanning calorimetry, and molecular dynamics simulations, we relate bulk melting measurements (\n                    <jats:italic>\n                      T\n                      <jats:sub>m<\/jats:sub>\n                    <\/jats:italic>\n                    (TCD\u2010COOH) = 56\u00b0C,\n                    <jats:italic>\n                      T\n                      <jats:sub>m<\/jats:sub>\n                    <\/jats:italic>\n                    (TCD\u2010OH) = 51\u00b0C,\n                    <jats:italic>\n                      T\n                      <jats:sub>m<\/jats:sub>\n                    <\/jats:italic>\n                    (TCD\u2010NH\n                    <jats:sub>2<\/jats:sub>\n                    ) = 26\u00b0C), to observed surface\u2010confined structural transitions. Across all monomers, polymerization efficiency increases above room temperature with a maximum near the onset of surface disorder or near solid\u2013solid transitions that alter distances between bond\u2010forming carbons (e.g., TCD\u2010OH herringbone phases):\n                    <jats:italic>\n                      T\n                      <jats:sub>max<\/jats:sub>\n                    <\/jats:italic>\n                    (TCD\u2010COOH) = 65\u00b0C,\n                    <jats:italic>\n                      T\n                      <jats:sub>max<\/jats:sub>\n                    <\/jats:italic>\n                    (TCD\u2010OH) = 45\u00b0C, and\n                    <jats:italic>\n                      T\n                      <jats:sub>ma<\/jats:sub>\n                    <\/jats:italic>\n                    <jats:sub>x<\/jats:sub>\n                    (TCD\u2010NH\n                    <jats:sub>2<\/jats:sub>\n                    ) = 45\u00b0C. These results demonstrate the relationship between optimal on\u2010surface reactivity and pre\u2010melting increases in alkyl chain mobility, establishing a broader strategy for maximizing on\u2010surface topochemical polymerization efficiency.\n                  <\/jats:p>","DOI":"10.1002\/smtd.70698","type":"journal-article","created":{"date-parts":[[2026,5,8]],"date-time":"2026-05-08T05:14:03Z","timestamp":1778217243000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Mapping Nanoscale Order\u2013Disorder Transitions to Optimal Topochemical Polymerization Across Alkyl Diacetylene Monolayers"],"prefix":"10.1002","volume":"10","author":[{"given":"Joseph A.","family":"Garfield","sequence":"first","affiliation":[{"name":"Department of Chemistry Purdue University  West Lafayette Indiana USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Soumya","family":"Paul","sequence":"additional","affiliation":[{"name":"Department of Chemistry Purdue University  West Lafayette Indiana USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shelley A.","family":"Claridge","sequence":"additional","affiliation":[{"name":"Department of Chemistry Purdue University  West Lafayette Indiana USA"},{"name":"Weldon School of Biomedical Engineering Purdue University  West Lafayette Indiana USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,5,7]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557\u2010019\u20100392\u20109"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja511995r"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1515\/znb\u20101969\u20100708"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/macp.1972.021540103"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197607641"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1660929"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3ra42639d"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1384554"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/la700241z"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2nr30245d"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.9b09600"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS01338B"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.colsurfa.2018.05.081"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3ra42639d"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF01549738"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202110517"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202004768"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202500926"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.8b03513"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35365B"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.253.5018.424"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1038\/204680a0"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.1c07428"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b05930"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC06466K"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp070998l"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.langmuir.6b03147"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c04534"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5NR00520E"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9FD00022D"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.3c16687"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CC00885F"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.0c08741"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.4c05086"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c22646"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.5c18718"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c12034"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.4c01106"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c09937"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/smll.202509179"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/pol.1955.120168222"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.66.2096"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.69.1395"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1039\/a701074e"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/a701071k"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.83.2362"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.carbon.2005.02.037"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/la900808f"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3212095"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.1c01377"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/la4049314"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199201891"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/nn800287x"},{"key":"e_1_2_8_55_1","first-page":"2332","article-title":"Topochemistry 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