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Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety
Authors:Kenji Hara  Keiji Iwahashi  Satoru Takakusagi  Kohei Uosaki  Masaya Sawamura
Institution:Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract:Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.
Keywords:Self-assembled monolayer (SAM)  Gold  Rhodium  X-ray photoelectron spectroscopy (XPS)
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