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However, achieving large birefringence (\u0394n) has largely depended on inorganic frameworks composed of metals with limited natural abundance or sustainability concerns. By contrast, organic cocrystals offer simple preparation and readily tunable packing. Here we design a series of diazapyrene derivatives and obtain 13 crystals, including three single\u2010component crystals and ten two\u2010component cocrystals formed separately with three distinct benzene derivatives, whose crystal\u2010packing anisotropy can be programmed to yield \u0394\n                    <jats:italic>n<\/jats:italic>\n                    \u00a0=\u00a00.152\u20131.269. Two compositions,\n                    <jats:bold>D27N<\/jats:bold>\n                    and\n                    <jats:bold>D13N<\/jats:bold>\n                    , combine suitable optical band gaps with exceptional birefringence (\u0394\n                    <jats:italic>n<\/jats:italic>\n                    = 1.223 and 1.269 at 546 nm, respectively), ranking among the highest reported for purely organic crystals, and under identical conditions, surpassing all reported inorganic birefringent crystals. Across the series, we uncover a Boltzmann\u2010type relationship between \u0394\n                    <jats:italic>n<\/jats:italic>\n                    and a geometric descriptor \u0394\n                    <jats:italic>S<\/jats:italic>\n                    (minimal\/maximal projected area of the conjugated core on crystallographic planes), thereby quantitatively linking molecular\u2010level packing anisotropy to macroscopic \u0394\n                    <jats:italic>n<\/jats:italic>\n                    . Cocrystal engineering also modulates second\u2010order nonlinear optical responses, including symmetry control and second\u2010harmonic generation tuning. This work establishes a metal\u2010free, designable route to high\u2010\u0394\n                    <jats:italic>n<\/jats:italic>\n                    optical crystals and provides a predictive metric for anisotropy\u2010driven materials discovery.\n                  <\/jats:p>","DOI":"10.1002\/anie.202524207","type":"journal-article","created":{"date-parts":[[2026,1,28]],"date-time":"2026-01-28T10:45:02Z","timestamp":1769597102000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.2"],"prefix":"10.1002","volume":"65","author":[{"given":"Lingyan","family":"Sun","sequence":"first","affiliation":[{"name":"Key Laboratory of Green Chemistry and Technology of Ministry of Education College of Chemistry, Sichuan University  Chengdu P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gangji","family":"Yi","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Chemistry and Technology of Ministry of Education College of Chemistry, Sichuan University  Chengdu P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guohong","family":"Zou","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Chemistry and Technology of Ministry of Education College of Chemistry, Sichuan University  Chengdu P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2233-7141","authenticated-orcid":false,"given":"Cheng","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Green Chemistry and Technology of Ministry of Education College of Chemistry, Sichuan University  Chengdu P.R. 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