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The resultant complexes were investigated for their magnetic properties in order to elucidate the impact of modification of the coordinating P\u2212O bond environment either by increasing steric bulk and\/or introduction of a third P\u2212N bond at the central phosphorus atom. Magnetic studies revealed substantial energy barriers (\n                    <jats:italic>U<\/jats:italic>\n                    <jats:sub>eff<\/jats:sub>\n                    ) of 640\u2005K and 491\u2005K for Dy compounds\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    , respectively, rendering them as some of the best\u2010performing air\u2010stable SIMs amongst the class of SIMs with\n                    <jats:italic>D<\/jats:italic>\n                    <jats:sub>5h<\/jats:sub>\n                    symmetry. Compounds\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    exhibit magnetization blocking (\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>B<\/jats:sub>\n                    ) at 6.5\u2005K and 6\u2005K, respectively, at a sweep rate of 20\u2005Oe\/s. Compound\n                    <jats:bold>1<\/jats:bold>\n                    benefits from increased lattice intermetallic distances due to bulky adamantyl substituent, but exhibits a significant deviation from linear axial (P)O\u2212Dy\u2212O(P) geometry (173.7(1)\u00b0). In addition to the deviation from linearity, the incorporation of a bulky adamantane (or carbazole) ligand in complex\n                    <jats:bold>1<\/jats:bold>\n                    (or\n                    <jats:bold>2<\/jats:bold>\n                    ) was found to result in relatively strong Dy\u2026H\u2212C agostic interactions, with distances of 3.698\u2005\u00c5 (3.376\u2005\u00c5). These interactions are expected to induce transverse anisotropy. Ab initio CASSCF\/RASSI\u2010SO\/SINGLE_ANISO calculations offer valuable insights into the dynamics of magnetic relaxation and the impact of axial bulkiness on the anisotropy of\n                    <jats:italic>D<\/jats:italic>\n                    <jats:sub>5h<\/jats:sub>\n                    systems. Beyond highlighting the crucial role of crystal field and symmetry in achieving high\u2010temperature SIMs, this study also explores how the secondary coordination sphere can be engineered to create novel SIMs.\n                  <\/jats:p>","DOI":"10.1002\/asia.202401477","type":"journal-article","created":{"date-parts":[[2025,1,2]],"date-time":"2025-01-02T07:24:42Z","timestamp":1735802682000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Unravelling the Role of Sterically Encumbered Ligands in Tuning the Magnetic Properties of Lanthanide\u2010Based\n                    <i>D<\/i>\n                    <sub>5h<\/sub>\n                    Single\u2010Ion Magnets"],"prefix":"10.1002","volume":"20","author":[{"given":"Aheli","family":"Ghatak","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology, Bombay  Powai 400076 Mumbai 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