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Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI<jats:sub>3<\/jats:sub> (<jats:italic>P\u20056<jats:sub>3<\/jats:sub><\/jats:italic>) and AsI<jats:sub>3<\/jats:sub> (<jats:italic>R\u20103<\/jats:italic>) undergo an intriguing transformation, leading to the emergence of six\u2010coordinated monoclinic phases (<jats:italic>C2\/m<\/jats:italic>) at 6\u2005GPa and 2\u2005GPa for PI<jats:sub>3<\/jats:sub> and AsI<jats:sub>3<\/jats:sub>, respectively. These high\u2010pressure phases exhibit their stability up to 10\u2005GPa for PI<jats:sub>3<\/jats:sub> and 12\u2005GPa for AsI<jats:sub>3<\/jats:sub>. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six\u2010coordinated octahedral BiI<jats:sub>3<\/jats:sub> crystal configuration observed at ambient conditions. Our investigation further underscores the pivotal role of pressure\u2010induced reactivity of the lone\u2010pair electrons in PI<jats:sub>3<\/jats:sub> and AsI<jats:sub>3<\/jats:sub>, facilitating their enhanced stereochemical reactivity and thereby enabling higher six\u2010fold coordination. Complementary analyses employing electron localization function (ELF) and density of states (DOS) effectively delineate the progression towards augmented coordination in PI<jats:sub>3<\/jats:sub> and AsI<jats:sub>3<\/jats:sub> with increasing pressure. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI<jats:sub>3<\/jats:sub> and BiI<jats:sub>3<\/jats:sub> under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.<\/jats:p>","DOI":"10.1002\/cphc.202400046","type":"journal-article","created":{"date-parts":[[2024,3,26]],"date-time":"2024-03-26T01:15:11Z","timestamp":1711415711000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Pressure Induces Six\u2010fold Coordination for the Lighter Pnictides Phosphorus and Arsenic Triiodide"],"prefix":"10.1002","volume":"25","author":[{"given":"Pranab","family":"Gain","sequence":"first","affiliation":[{"name":"School of Chemical Sciences Indian Association for the Cultivation of Science  2\u2005A and 2B Raja S. 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