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However, the direct self\u2010assembly of photothermal nanomaterials absorbed in biological transparent window and control over their absorption properties through aggregation behavior remains a grand challenge. Here, the control over superlarge absorption redshift (ranging from 105 nm to 150 nm) of mono\u2010\u03b1\u2010substituted carboxy zinc phthalocyanine (\u03b1ZnPc) through kinetic assembly methodologies is demonstrated, resulting in the fabrication of photothermal nanoagents within tissue\u2010transparent NIR window. Tailoring the solvent polarity allows for the manipulation of kinetic pathways, leading to a variety of self\u2010assembled structures exhibiting distinct \u03b1ZnPc macrocycle stacking modes that attribute to their different absorption redshift properties. Mechanistic studies of the relationship between solvent polarity and pathway complexity revealed the energy landscape that governs the unique kinetic behavior. The specific stacking mode and conformation conforming to the charge\u2010transfer model within these \u03b1ZnPc assembled structures have been revealed by theoretical calculations. Crucially, the \u03b1ZnPc nanostructures show remarkable physiological stability and robust photothermal performances within biological transparent window, efficiently ablating primary tumors and triggering immunogenic cell death. This effect is further augmented by the immunomodulatory effects of thymopentin, exhibiting vaccine\u2010like capabilities in suppressing the growth of distant tumors. This research demonstrates unprecedented levels of control over supramolecular structures and their superlarge red\u2010shifted absorption, providing great opportunities for future design and construction of supramolecular NIR materials with fascinating properties toward cancer treatments.<\/jats:p>","DOI":"10.1002\/adhm.202403494","type":"journal-article","created":{"date-parts":[[2025,2,14]],"date-time":"2025-02-14T06:30:58Z","timestamp":1739514658000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Control Over Kinetic Self\u2010Assembly of Phthalocyanine into Photothermal Nano\u2010Vaccine Enabling Tunable Superlarge Absorption Redshift"],"prefix":"10.1002","volume":"14","author":[{"given":"Shuo","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1874-031X","authenticated-orcid":false,"given":"Yongxin","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jilu","family":"Zheng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chunlei","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chunyang","family":"Diao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Luyang","family":"Zhao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Biochemical Engineering Institute of Process Engineering Chinese Academy of Sciences  Beijing 100190 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chunzhao","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Bio\u2010fibers and Eco\u2010textiles Institute of Biochemical Engineering The Affiliated Qingdao Central Hospital of Qingdao University College of Materials Science and Engineering Qingdao University  Qingdao 266071 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