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The pristine crystals of monomer\n                    <jats:bold>1<\/jats:bold>\n                    upon topochemical azide\u2010alkyne cycloaddition (TAAC) reaction give a 1\u2009:\u20091 blend of 1,4\u2010 and 1,5\u2010triazole\u2010linked polymers due to the presence of two self\u2010sorted reactive conformers in the crystal. We designed a binary isomorphous cocrystal of monomer\n                    <jats:bold>1<\/jats:bold>\n                    and a structurally similar dummy molecule\n                    <jats:bold>2<\/jats:bold>\n                    to limit the number of reactive conformers of\n                    <jats:bold>1<\/jats:bold>\n                    to one and thus to get one type of polymer. Equimolar solution of\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    in chloroform\u2010acetone mixture gave two 1\u2009:\u20091 cocrystals\n                    <jats:bold>Co\u2010I<\/jats:bold>\n                    and\n                    <jats:bold>Co\u2010II<\/jats:bold>\n                    . The\n                    <jats:bold>Co\u2010II<\/jats:bold>\n                    , a chloroform adduct, on heating undergoes desolvation and polymorphic transition to\n                    <jats:bold>Co\u2010I<\/jats:bold>\n                    .\n                    <jats:bold>Co\u2010I<\/jats:bold>\n                    is isomorphic to\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    and possess self\u2010sorted arrays of\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    . Heating\n                    <jats:bold>Co\u2010I<\/jats:bold>\n                    results in the TAAC polymerization giving 1,4\u2010triazolyl\u2010linked polymer of\n                    <jats:bold>1<\/jats:bold>\n                    selectively, showing the power of crystal engineering in regiocontrol.\n                  <\/jats:p>","DOI":"10.1002\/anie.202210733","type":"journal-article","created":{"date-parts":[[2022,8,10]],"date-time":"2022-08-10T13:00:05Z","timestamp":1660136405000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Tuning the Regioselectivity of Topochemical Polymerization through Cocrystallization of the Monomer with an Inert Isostere"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9801-7772","authenticated-orcid":false,"given":"Kuntrapakam","family":"Hema","sequence":"first","affiliation":[{"name":"School of Chemistry IISER Thiruvananthapuram Kerala 695551 India"},{"name":"Present address: Department of Molecular Chemistry and Materials Science Weizmann Institute of Science Rehovot 7610001 Israel"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8416-9764","authenticated-orcid":false,"given":"Cijil","family":"Raju","sequence":"additional","affiliation":[{"name":"School of Chemistry IISER Thiruvananthapuram Kerala 695551 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0385-0604","authenticated-orcid":false,"given":"Subhrajyoti","family":"Bhandary","sequence":"additional","affiliation":[{"name":"Department of Chemistry Ghent University Krijgslaan 281-S3 9000 Ghent Belgium"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4005-3655","authenticated-orcid":false,"given":"Kana M.","family":"Sureshan","sequence":"additional","affiliation":[{"name":"School of Chemistry IISER Thiruvananthapuram Kerala 695551 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,8,29]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35343A"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00840K"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00057a001"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC07066A"},{"key":"e_1_2_3_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC08374E"},{"key":"e_1_2_3_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.2c00128"},{"key":"e_1_2_3_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202114089"},{"key":"e_1_2_3_7_2","doi-asserted-by":"crossref","first-page":"e202114089","DOI":"10.1002\/ange.202114089","volume":"134","year":"2022","journal-title":"Angew. 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