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In this study, a novel chalcohalide, Cs<jats:sub>4<\/jats:sub>Zn<jats:sub>5<\/jats:sub>P<jats:sub>6<\/jats:sub>S<jats:sub>18<\/jats:sub>I<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>) is successfully synthesized, by incorporating the highly electropositive Cs and the large electronegative I element into the zinc thiophosphate. Its 3D open framework features an edge\u2010shared by distorted [ZnS<jats:sub>4<\/jats:sub>], ethanol\u2010like [P<jats:sub>2<\/jats:sub>S<jats:sub>6<\/jats:sub>], and unusual [ZnS<jats:sub>2<\/jats:sub>I<jats:sub>2<\/jats:sub>] polyhedrons, which is inconsistent with the soft\u2010hard\u2010acids\u2010bases theory. Remarkably, compound <jats:bold>1<\/jats:bold> simultaneously exhibits the large second\u2010harmonic generation (SHG, 1.1\u00d7AgGaS<jats:sub>2<\/jats:sub>, @1.3\u00a0\u00b5m) and a wide band gap (3.75\u00a0eV) toward a high laser\u2010induced damage threshold (16.7\u00d7AgGaS<jats:sub>2<\/jats:sub>, @1.06\u00a0\u00b5m), satisfying the rigorous requirements for a prominent infrared NLO material with concurrent SHG intensity (\u22650.5\u00d7AGS) and band gap (\u22653.5\u00a0eV). Moreover, to the best of the knowledge, the experimental result shows that phase <jats:bold>1<\/jats:bold> has the largest birefringence (0.108, @546\u00a0nm) in chalcohalide and meets phase\u2010matching behavior demand originating from the polarizable anisotropy of NLO\u2010functional motifs. This finding may provide great opportunities for designing birefringent chalcohalides.<\/jats:p>","DOI":"10.1002\/smll.202303847","type":"journal-article","created":{"date-parts":[[2023,7,19]],"date-time":"2023-07-19T04:35:07Z","timestamp":1689741307000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":22,"title":["Cs<sub>4<\/sub>Zn<sub>5<\/sub>P<sub>6<\/sub>S<sub>18<\/sub>I<sub>2<\/sub>: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs"],"prefix":"10.1002","volume":"19","author":[{"given":"Xian\u2010Dan","family":"Chai","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian 350002 P. R. 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