4 research outputs found
Substituent Parameters Impacting Isomer Composition and Optical Properties of Dihydroindolizine Molecular Switches
In
an attempt to understand which factors influence constitutional
isomer control of 6â˛- and 8â˛-substituted dihydroindolizines
(DHIs), a series of asymmetric pyridines was condensed with dimethyl
spiroÂ[cycloprop[2]Âene-1,9â˛-fluorene]-2,3-dicarboxylate. The
substituents on the pyridial derivatives ranged from donating to withdrawing
and demonstrated control over the isomeric ratios for all DHIs. Substituent
control proved to be selective for the highly donating amino, which
exclusively formed the 8Ⲡisomer. The same ratios were reproduced
via photolytic experiments, which suggested that the condensation
reaction is dominated by the productâs thermodynamic stability.
The electronic influences of the substituents extends beyond isomer
control, as it impacts the DHIsâ optical properties and electrocyclization
(switching) rates to the spiro conformers. Our results allow us to
predict the syntheses and properties of future 6â˛- or 8â˛-substituted
DHIs, molecules that will be applied in understanding the role of
the dipole vector orientation to work function switching
Spectroscopic Evidence of Work Function Alterations Due to Photoswitchable Monolayers on Gold Surfaces
Taking advantage of surfacesâ
response to interfacial dipoles,
a class of photochromophores (dihydroindolizine) is demonstrated to
alter the work function of the underlying substrate (âź170 meV).
This same molecule also provides spectroscopic signatures for correlating
the change in molecular structure to the induced change in the surfacesâ
electronic properties. Polarization modulation infrared reflection
absorption spectroscopy (PM-IRRAS) allows analysis of the characteristic
dihydroindolizine CîťC (1559 cm<sup>â1</sup>) and pyridinium
(1643 cm<sup>â1</sup>) stretch as a function of photoexcitation.
Structural assignments of this photochromophore are corroborated to
density function theory calculations. Conformational changes in the
monolayers appear in parallel with work function changes and are consistent
with both its rate and magnitude