Unlocking n-alk-1-ynes Conformers: Quantum "Trigger Finger" versus "Stiff Joint" Conformations

TL;DR

This study reveals two nearly equal-energy conformers in n-alk-1-ynes with high rotational barriers, introducing the concepts of 'Quantum Trigger Finger' and 'Stiff Joint' conformations that impact spectroscopic analysis and molecular electronics.

Contribution

It uncovers the existence of two near-isoenergetic rotamers in n-alk-1-ynes and explains their kinetic and electronic stabilization, providing new insights into their conformational behavior.

Findings

Two rotamers with ~50:50 population ratio identified.

High rotational barrier (~150 meV) prevents rapid interconversion.

Conformational ensemble affects spectroscopic data interpretation.

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 (C$_s$) and skewed (C$_1$). The high, symmetric rotational energy barrier ($\approx 150$\,meV) arises from unique steric relief near the $\mathrm{sp}$ center coupled with electronic stabilization of C$_1$. This creates a unique kinetic profile: a Quantum ``Trigger Finger'' ($\alpha$ rotation) that enforces an $\approx 50\%:\,50\%$ $\mathrm{C}_s/\mathrm{C}_1$ ensemble, sharply contrasting with the thermodynamically biased ``Stiff Joint'' ($\delta$ 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.