Lateral dipole moments induced by all-cis-pentafluorocyclohexyl groups cause unanticipated effects in self-assembled monolayers  

作　　者：Christian Fischer Saunak Das Qingzhi Zhang Yangbiao Liu Lothar Weinhardt David O’Hagan Michael Zharnikov Andreas Terfort 

机构地区：[1]Institute of Inorganic and Analytical Chemistry,Goethe University Frankfurt,Max-von-Laue-Straße 7,60438 Frankfurt am Main,Germany [2]Applied Physical Chemistry,Heidelberg University,Im Neuenheimer Feld 253,69120 Heidelberg,Germany [3]School of Chemistry,University of St Andrews,North Haugh,St Andrews,Fife,KY169ST,UK [4]Institute for Photon Science and Synchrotron Radiation,Karlsruhe Institute of Technology(KIT),Hermann-v.-Helmholtz-Platz 1,76344 Eggenstein-Leopoldshafen,Germany [5]Institute for Chemical Technology and Polymer Chemistry(ITCP),Karlsruhe Institute of Technology(KIT),Engesserstr.18/20,76128 Karlsruhe,Germany [6]Department of Chemistry and Biochemistry,University of Nevada,Las Vegas(UNLV),4505 Maryland Parkway,Las Vegas,NV 89154-4003,USA

出　　处：《Nano Research》2023年第8期11030-11041,共12页纳米研究（英文版）

摘　　要：All-cis-hexafluoro-and all-cis-pentafluoro-cyclohexane(PFCH)derivatives are new kinds of materials,the structures and properties of which are dominated by the highly dipolar Janus-face motif.Here,we report on the effects of integrating the PFCH groups into self-assembled monolayers(SAMs)of alkanethiolates on Au(111).Monolayers with an odd(eleven)and even(twelve)number of methylene groups were characterized in detail by several complementary experimental tools,supported by theoretical calculations.Surprisingly,all the data show a high similarity of both kinds of monolayers,nearly lacking the typically observed odd-even effects.These new monolayers have a packing density about 1/3 lower than that of non-substituted alkanethiolate monolayers,caused by the bulkiness of the PFCH moieties.The orientations of the PFCH groups and the alkyl chains could be determined independently,suggesting a conformation similar to the one found in the solid state structure of an analogous compound.Although in the SAMs the PFCH groups are slightly tilted away from the surface normal with the axial fluorine atoms pointing downwards,most of the dipole moments of the group remain oriented parallel to the surface,which is a unique feature for a SAM system.The consequences are much lower water contact angles compared to other partly fluorinated SAMs as well as rather moderate work function values.The interaction between the terminal PFCH moieties results in an enhanced stability of the PFCH-decorated SAMs toward exchange reaction with potential molecular substituents in spite of the lower packing density of these films.

关 键 词：odd-even-effects work function self-assembled monolayer(SAM) kinetic stability infrared-reflection absorption spectroscopy X-ray photoelectron spectroscopy 

分 类 号：O62[理学—有机化学]