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An area-demanding tripodal trithiol containing six peripheral methyl groups was synthesized, and its selfassembled monolayer (SAM) was formed onto a Au(111) surface, which was electrochemically characterized. The SAM showed a significant lowering of the surface coverage due to the bulkiness of the methyl groups, as demonstrated by the charge of reductive elimination. The experimentally determined surface density was aptly reproduced by density functional theory (DFT) calculations under periodic boundary conditions.

Tuning the coverage of self-assembled monolayer by introducing bulky substituents onto rigid adamantane tripod