{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T08:18:29Z","timestamp":1787818709095,"version":"build-2784847793"},"reference-count":36,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T00:00:00Z","timestamp":1787788800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T00:00:00Z","timestamp":1787788800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22575122"],"award-info":[{"award-number":["22575122"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004608","name":"Natural Science Foundation of Jiangsu Province","doi-asserted-by":"publisher","award":["SBK2023030008"],"award-info":[{"award-number":["SBK2023030008"]}],"id":[{"id":"10.13039\/501100004608","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The development of nitrogen\u2010rich fused azaarenes with exceptional thermal stability remains a critical challenge because the incorporation of high\u2010energy N\u2500N and N\u2550N linkages typically compromises molecular stability. Herein, we report a metal\u2010free oxidative annulation strategy for the construction of an ultrathermostable pyrazole\u2010fused azaarene (\n                    <jats:bold>TYX\u201040<\/jats:bold>\n                    ) through concurrent N\u2550N and C\u2500C bond formation from a simple aminopyrazole precursor. Using hydrogen peroxide as a green oxidant under mild conditions, this transformation enables direct self\u2010coupling of 3,5\u2010diamino\u20101\n                    <jats:italic>H<\/jats:italic>\n                    \u2010pyrazole to furnish a highly conjugated [5,6,5]\u2010fused nitrogen\u2010rich framework (\n                    <jats:bold>TYX\u201040<\/jats:bold>\n                    ) without transition\u2010metal catalysis. Mechanistic investigations, including radical\u2010trapping experiments and density functional theory calculations, support a radical\u2010mediated sequential annulation pathway involving oxidative azo formation followed by intramolecular C\u2500C coupling. Benefiting from its highly planar and symmetric fused\u2010ring architecture,\n                    <jats:bold>TYX\u201040<\/jats:bold>\n                    exhibits exceptional thermal stability with a decomposition temperature of 414\u00b0C, among the highest values reported for nitrogen\u2010rich fused heterocycles. Computational analyses reveal that enhanced aromatic delocalization and uniform electronic distribution play critical roles in stabilizing the fused azaarene framework.\n                  <\/jats:p>","DOI":"10.1002\/smll.75521","type":"journal-article","created":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T07:39:22Z","timestamp":1787816362000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Metal\u2010Free Oxidative Annulation toward an Ultrathermostable Nitrogen\u2010Rich Fused Azaarene"],"prefix":"10.1002","author":[{"given":"Mingjie","family":"Tang","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2558-5896","authenticated-orcid":false,"given":"Yuji","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chuan","family":"Xiao","sequence":"additional","affiliation":[{"name":"China Northern Industries Group Co., Ltd (NORINCO Group)  Beijing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chunhui","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiwei","family":"Zeng","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4376-4639","authenticated-orcid":false,"given":"Wei","family":"Huang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0501-6469","authenticated-orcid":false,"given":"Guangbin","family":"Cheng","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-8104-8617","authenticated-orcid":false,"given":"Peng\u2010fei","family":"Cui","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9549-9195","authenticated-orcid":false,"given":"Yongxing","family":"Tang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Nanjing University of Science and Technology  Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,27]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5c00621"},{"key":"e_1_2_8_3_1","doi-asserted-by":"crossref","first-page":"30447","DOI":"10.1021\/jacs.5c10598","article-title":"The Action of Plastic Degrading Enzyme Is Accelerated Mainly due to an Increase in Thermal Stability Rather than by an Inherent Catalytic Effect","volume":"147","author":"Nandi A.","year":"2025","journal-title":"Journal of the American Chemical Society"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5c00232"},{"key":"e_1_2_8_5_1","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1021\/acscentsci.9b01096","article-title":"Molecular and Crystal Features of Thermostable Energetic Materials: Guidelines for Architecture of \u2018Bridged\u2019 Compounds","volume":"6","author":"Li H.","year":"2020","journal-title":"ACS Central Science"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/s42114\u2010025\u201001356\u20104"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2010.04.120"},{"key":"e_1_2_8_8_1","doi-asserted-by":"crossref","first-page":"8619","DOI":"10.1002\/chem.201600769","article-title":"Synthesis and Investigation of 2,6\u2010Bis(picrylamino)\u20103,5\u2010dinitro\u2010pyridine (PYX) and Its Salts","volume":"22","author":"Klap\u00f6tke T. 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