Oligomers consisting of aromatic building blocks separated by alkynyl units were synthesized by Sonogashira cross-coupling of aryl halides with terminal acetylenes. Strong electron acceptors such as -F and -CF3 and weak electron donors like -CH3 were placed as substituents on one of the benzene rings. Acetyl-protected sulfhydryl groups were attached to one end of these molecules to promote their self-organization on gold surfaces. The electron-transport properties of such self-assembled monolayers (SAMs) are highly sensitive to the local order of the molecules in the solid state. Single crystals were analyzed by X-ray diffraction experiments that revealed structural details that could lead to a better understanding of the electron-transport properties. The unsymmetrical substitution of the aromatic rings by electron-active groups in the ortho-, meta-, or para positions resulted in changes of such molecular parameters as bonding and torsion angles and planarity. These parameters, in turn, can affect the angle of the molecular attachment to a gold substrate and the density of the resulting SAMS. Patterned SAMS of some of these molecules and comparison alkane thiols were obtained on gold by microcontact printing or flooding. The SAM thickness was determined by spectroscopic ellipsometry. Surface potential differences between adjacent SAMS or between SAMS and the gold substrate were measured by scanning surface potential microscopy under ambient conditions. (C) 2003 Wiley Periodicals, Inc.