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However, their NLO performance is fundamentally restricted by the limited structural polarization inherent to traditional pseudo\u2010octahedral coordination. In this work, we demonstrate the feasibility of using highly polar tricoordinate trigonal pyramids to overcome the thermodynamic constraints of the octahedral cages, enabling a structural shift from symmetric hexacoordination to discrete structures, thus enhancing second harmonic generation (SHG). By introducing the massive steric hindrance of the chiral\n                    <jats:italic>R\/S<\/jats:italic>\n                    \u20101,2,3,4\u2010tetrahydro\u20101\u2010naphthylamine (\n                    <jats:italic>R\/S<\/jats:italic>\n                    \u2010THNA) cation with the intrinsic stereochemical activity of the Ge\n                    <jats:sup>2+<\/jats:sup>\n                    4\n                    <jats:italic>s<\/jats:italic>\n                    <jats:sup>2<\/jats:sup>\n                    lone pair, we synthesized chiral germanium halides, (\n                    <jats:italic>R\/S<\/jats:italic>\n                    \u2010THNA)GeX\n                    <jats:sub>3<\/jats:sub>\n                    (X = Br, I). Crystallographic and topological analyses confirm the complete cleavage of secondary Ge\u00b7\u00b7\u00b7X interactions, yielding isolated [GeX\n                    <jats:sub>3<\/jats:sub>\n                    ]\n                    <jats:sup>\u2212<\/jats:sup>\n                    chromophores. Furthermore, guided by transition dipole moment calculations, (\n                    <jats:italic>R<\/jats:italic>\n                    \u2010THNA)GeI\n                    <jats:sub>1.75<\/jats:sub>\n                    Br\n                    <jats:sub>1.25<\/jats:sub>\n                    was constructed via a mixed\u2010halide strategy. Single\u2010crystal SHG measurements reveal that (\n                    <jats:italic>R<\/jats:italic>\n                    \u2010THNA)GeI\n                    <jats:sub>1.75<\/jats:sub>\n                    Br\n                    <jats:sub>1.25<\/jats:sub>\n                    achieves an exceptional response, being 1.66 and 9.44 times those of (\n                    <jats:italic>R<\/jats:italic>\n                    \u2010THNA)GeI\n                    <jats:sub>3<\/jats:sub>\n                    and (\n                    <jats:italic>R<\/jats:italic>\n                    \u2010THNA)GeBr\n                    <jats:sub>3<\/jats:sub>\n                    crystals, respectively. Standard Kurtz\u2013Perry measurements of (\n                    <jats:italic>R<\/jats:italic>\n                    \u2010THNA)GeI\n                    <jats:sub>1.75<\/jats:sub>\n                    Br\n                    <jats:sub>1.25<\/jats:sub>\n                    at a 125\u2013150\u00a0\u00b5m particle size reveal a powder SHG efficiency of 3.06 times that of KH\n                    <jats:sub>2<\/jats:sub>\n                    PO\n                    <jats:sub>4<\/jats:sub>\n                    , representing a highly competitive value in chiral germanium halides. This work establishes a rational paradigm for designing high\u2010performance NLO materials through precise coordination tailoring.\n                  <\/jats:p>","DOI":"10.1002\/anie.8413238","type":"journal-article","created":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T10:25:50Z","timestamp":1788258350000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chiral Trigonal Pyramidal Germanium Halides for Enhanced Second Harmonic Generation"],"prefix":"10.1002","volume":"65","author":[{"given":"Jia","family":"Zhang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Advanced Chemical Power Sources Frontiers Science Center For New Organic Matter Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Academy For Advanced Interdisciplinary Studies School of Materials Science and Engineering College of Chemistry Nankai University  Tianjin P. R. 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