Micrometer and nanometer scale patterning using the photo-fries rearrangement: toward selective execution of molecular transformations with nanoscale spatial resolution.
The photolithographic modification of monolayers provides a versatile and powerful means of fabricating functionalized nanostructured surfaces. In this contribution, we present photosensitive thiol-bearing aryl ester groups which are capable of undergoing the so-called photo-Fries rearrangement to yield hydroxyketones. Phenyl 16-mercaptohexadecanoate was prepared by a three-step synthesis. This molecule undergoes a photoisomerization reaction upon illumination with UV light at ca. 250 nm. Subsequently this molecule was applied as a self-assembled monolayer on gold. Following photochemical modification, the adsorbates were selectively derivatized to yield amino-functionalized surfaces using a simple two-step reaction. This reaction was monitored by X-ray photoelectron spectroscopy and contact angle measurements and friction force microscopy. Micrometer-scale patterned surfaces were produced using a contact mask in conjunction with a frequency-doubled argon ion laser (lambda=244 nm). Near-field optical exposure was carried out by coupling the laser to a scanning near-field optical microscope and yielded nanometer-scale resolution. Following derivatization, the resulting structures were analyzed by friction force microscopy. Clear contrast was observed in the friction signal following surface modification.
Griesser
Thomas
T
Institute for Chemistry and Technology of Materials (ICTM), Graz University of Technology, Stremayrgasse 16, 8010 Graz, Austria.
Adams
Joseph
J
Wappel
Julia
J
Kern
Wolfgang
W
Leggett
Graham J
GJ
Trimmel
Gregor
G