Unlocking n ‐alk‐1‐ynes conformers: Quantum “trigger finger” versus “stiff joint” conformations

Abstract Molecular conformation in n ‐alk‐1‐ynes (CnA) is conventionally simplified to an all‐planar structure. We report a comprehensive quantum chemical analysis revealing two near‐isoenergetic rotamers at the acetylenic terminus: planar () and skewed (). The high, symmetric rotational energy barrier ( meV) arises from unique steric relief near the center coupled with electronic stabilization of . This creates a unique kinetic profile: a Quantum “Trigger Finger” ( rotation) that enforces an ensemble, sharply contrasting with the thermodynamically biased “Stiff Joint” ( rotation) of the alkyl chain. This structural degeneracy necessitates ensemble averaging for spectroscopic data interpretation, while the slow interconversion permits kinetic trapping and intentional conformer enrichment during synthesis and molecular junction fabrication. Our work redefines the alkyne anchor, providing a blueprint for accurate interpretation of spectroscopic data and achieving conformational control in molecular electronics.