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¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...

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The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.

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Introduction
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Nanometer Confinement Induces Nematic Order in 1-Dodecanol.

Antonela Ananiadou¹, George Papamokos¹, Martin Steinhart²

¹Department of Physics, University of Ioannina, P.O. Box 1186, 451 10 Ioannina, Greece.

The Journal of Physical Chemistry. B

|November 13, 2020

Summary

Confinement alters 1-dodecanol's phase behavior, suppressing its bulk rotator phase. Instead, a nematic liquid crystalline phase forms in nanopores, with phase transitions dependent on pore size.

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Area of Science:

Materials Science
Physical Chemistry
Nanotechnology

Background:

1-dodecanol exhibits a rotator phase in bulk conditions.
Nanoconfinement significantly influences molecular phase behavior and dynamics.
Understanding phase transitions in confined systems is crucial for materials design.

Purpose of the Study:

To investigate the phase state and molecular dynamics of 1-dodecanol under nanometer confinement.
To determine the impact of nanoporous alumina templates on 1-dodecanol's phase transitions.
To map the phase diagram of 1-dodecanol within confined geometries.

Main Methods:

Utilized self-ordered nanoporous alumina templates for nanoconfinement.
Employed temperature-dependent dielectric permittivity measurements.
Conducted X-ray diffraction analysis to study phase transitions.
Investigated molecular dynamics in bulk and confined 1-dodecanol.

Main Results:

The rotator phase observed in bulk 1-dodecanol is absent under confinement.
A nematic liquid crystalline phase emerges in pores ranging from 400 to 25 nm in diameter.
Phase transitions (nematic-to-isotropic, crystalline-to-nematic) were identified and their limits determined.
Pores below 20 nm facilitate a direct liquid-to-crystalline phase transition.

Conclusions:

Nanoconfinement fundamentally alters the phase behavior of 1-dodecanol, replacing the rotator phase with a nematic liquid crystalline phase.
The pore size dictates the accessible phase diagram and transition pathways.
Dielectric properties provide insights into the molecular dynamics and phase fingerprint of confined 1-dodecanol.