nl8b00949_si_001.pdf (3.04 MB)
Label-Free Dynamic Detection of Single-Molecule Nucleophilic-Substitution Reactions
journal contribution
posted on 2018-06-06, 00:00 authored by Chunhui Gu, Chen Hu, Ying Wei, Dongqing Lin, Chuancheng Jia, Mingzhi Li, Dingkai Su, Jianxin Guan, Andong Xia, Linghai Xie, Abraham Nitzan, Hong Guo, Xuefeng GuoThe
mechanisms of chemical reactions, including the transformation
pathways of the electronic and geometric structures of molecules,
are crucial for comprehending the essence and developing new chemistry.
However, it is extremely difficult to realize at the single-molecule
level. Here, we report a single-molecule approach capable of electrically
probing stochastic fluctuations under equilibrium conditions and elucidating
time trajectories of single species in non-equilibrated systems. Through
molecular engineering, a single molecular wire containing a functional
center of 9-phenyl-9-fluorenol was covalently wired into nanogapped
graphene electrodes to form stable single-molecule junctions. Both
experimental and theoretical studies consistently demonstrate and
interpret the direct measurement of the formation dynamics of individual
carbocation intermediates with a strong solvent dependence in a nucleophilic-substitution
reaction. We also show the kinetic process of competitive transitions
between acetate and bromide species, which is inevitable through a
carbocation intermediate, confirming the classical mechanism. This
unique method creates plenty of opportunities for carrying out single-molecule
dynamics or biophysics investigations in broad fields beyond reaction
chemistry through molecular design and engineering.
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biophysics investigationsnucleophilic-substitution reactionsingle-molecule approachelucidating time trajectories9- phenyl -9-fluorenolbromide speciesLabel-Free Dynamic Detectionmechanismsingle-molecule levelreaction chemistryequilibrium conditionsnon-equilibrated systemssingle-molecule dynamicsformation dynamicschemical reactionssingle-molecule junctionsSingle-Molecule Nucleophilic-Substitution Reactionsnanogapped graphene electrodescarbocation intermediatestransformation pathways
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