posted on 2022-12-22, 19:06authored byBrittany
L. Huffman, Gabriella P. Bein, Hala Atallah, Carrie L. Donley, Reem T. Alameh, Jonathan P. Wheeler, Nicolas Durand, Alexis K. Harvey, Matthew C. Kessinger, Cindy Y. Chen, Zahra Fakhraai, Joanna M. Atkin, Felix N. Castellano, Jillian L. Dempsey
A sonochemical-based hydrosilylation method was employed
to covalently
attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO)3Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline)
was reacted with hydrogen-terminated silicon(111) in an ultrasonic
bath to generate a hybrid photoelectrode. Subsequent reaction with
1-hexene enabled functionalization of remaining atop Si sites. Attenuated
total reflectance–Fourier transform infrared spectroscopy confirms
attachment of the organometallic complex to silicon without degradation
of the organometallic core, supporting hydrosilylation as a strategy
for installing coordination complexes that retain their molecular
integrity. Detection of Re(I) and nitrogen by X-ray photoelectron
spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO)3Cl. Cyclic
voltammetry and electrochemical impedance spectroscopy under white
light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO)3Cl undergoes two electron
reductions. Mott–Schottky analysis indicates that the flat
band potential is 239 mV more positive for p-Si(111) co-functionalized
with both fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene than when functionalized with 1-hexene alone.
XPS, ultraviolet photoelectron spectroscopy, and Mott–Schottky
analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene introduces
a negative interfacial dipole, facilitating reductive photoelectrochemistry.