Directing isomerization reactions of cumulenes with electric fields

Zang, Yaping; Zou, Qi; Fu, Tianren; Ng, Fay; Fowler, Brandon; Yang, Jingjing; Li, Hexing; Steigerwald, Michael L.; Nuckolls, Colin; Venkataraman, Latha

doi:10.1038/s41467-019-12487-w

Directing isomerization reactions of cumulenes with electric fields

Journal Article · Wed Oct 02 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-12487-w· OSTI ID:1624197

Zang, Yaping ^[1]; ^[2]; Fu, Tianren ^[3]; Ng, Fay ^[3]; Fowler, Brandon ^[3]; Yang, Jingjing ^[3]; Li, Hexing ^[4]; Steigerwald, Michael L. ^[3]; ^[3]; ^[3]

Columbia Univ., New York, NY (United States); DOE/OSTI
Columbia Univ., New York, NY (United States); Shanghai Univ. of Electric Power (China)
Columbia Univ., New York, NY (United States)
Shanghai Univ. of Electric Power (China)

Electric fields have been proposed as having a distinct ability to catalyze chemical reactions through the stabilization of polar or ionic intermediate transition states. Although field-assisted catalysis is being researched, the ability to catalyze reactions in solution using electric fields remains elusive and the understanding of mechanisms of such catalysis is sparse. Here we show that an electric field can catalyze the cis-to-trans isomerization of [3]cumulene derivatives in solution, in a scanning tunneling microscope. We further show that the external electric field can alter the thermodynamics inhibiting the trans-to-cis reverse reaction, endowing the selectivity toward trans isomer. Using density functional theory-based calculations, we find that the applied electric field promotes a zwitterionic resonance form, which ensures a lower energy transition state for the isomerization reaction. The field also stabilizes the trans form, relative to the cis, dictating the cis/trans thermodynamics, driving the equilibrium product exclusively toward the trans.

View Accepted Manuscript (DOE)

Research Organization:: Columbia Univ., New York, NY (United States); Columbia University, New York, NY (United States)

Sponsoring Organization:: Columbia University; National Science Foundation (NSF); Shanghai University of Electric Power; USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0019440

OSTI ID:: 1624197

Alternate ID(s):: OSTI ID: 2202968

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 10; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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