Relating Electron Donor and Carboxylic Acid Anchoring Substitution Effects in Azo Dyes to Dye-Sensitized Solar Cell Performance

The
relationship between the molecular structures of a series of
azo dyes and their operational performance when applied to dye-sensitized
solar cells (DSSCs) is probed via experimental and computational analysis.
Seven azo dyes, with three different donating groups (dimethylamino,
diethylamino, and dipropylamino)
and carboxylic acid anchoring positions (ortho-, meta-, and para-substituted phenyl rings)
are studied. Single-crystal X-ray diffraction is employed in order
to analyze the effects of conformation and quantify the contribution
of quinoidal resonance forms to the intramolecular charge transfer
(ICT), which controls their intrinsic photovoltaic potential from
an electronic standpoint. Harmonic oscillator stabilization energy
(HOSE) calculations indicate that the para- and ortho-azo dyes exhibit potential for DSSC application. However,
from a geometrical standpoint, the crystal structure data, proton
nuclear magnetic resonance spectroscopy (1H NMR), and density
functional theory (DFT) all indicate that intramolecular hydrogen
bonds form in ortho-dyes within both solid and solution
states, impeding their intrinsic ICT-based photovoltaic potential,
and offering insights into the photostability of azo dyes and the
dye···TiO2 anchoring mechanism in DSSCs.
Donor effects are manifested in the packing mode and molecular planarity
revealed by X-ray crystallography and in the UV/vis absorption spectra.
DFT and time-dependent density functional theory (TDDFT) were performed
to understand the electronic and optical properties of these azo dyes;
these calculations compare well with experimental findings. Operational
tests of DSSCs, functionalized by these azo dyes, show that the carboxylic
acid anchoring position plays a crucial role in DSSC performance,
while donating groups offer a much less obvious effect on the overall
DSSC device efficiency.