TY - JOUR
T1 - A Benchtop Method for Appending Protic Functional Groups to N-Heterocyclic Carbene Protected Gold Nanoparticles
AU - DeJesus, Joseph F.
AU - Sherman, Lindy M.
AU - Yohannan, Darius J.
AU - Becca, Jeffrey C.
AU - Strausser, Shelby L.
AU - Karger, Leonhard F.P.
AU - Jensen, Lasse
AU - Jenkins, David M.
AU - Camden, Jon P.
N1 - Funding Information:
This material is based on work supported by the National Science Foundation under grant numbers CHE-1709881 (D.J.Y., L.M.S., and J.P.C.), CHE-1709468 (J.F.D., S.L.S, and D.M.J.), CHE-1362825, and NRT-1449785 (J.C.B., and L.J.). L.F.P.K. thanks the German Academic Exchange Service for funding. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. Portions of this work were conducted with Advanced Cyberinfrastructure computational resources provided by The Institute for Cyber-Science at The Pennsylvania State University (http://ics.psu.edu). J.P.C., D.J.Y., and S.L.S., wish to thank John Dunlap for assistance with the SEM and TEM measurements. J.P.C. and L.M.S. thank the ND Energy Materials Characterization Facility (MCF) for assistance with the XPS experiments. The MCF is funded by the Sustainable Energy Initiative (SEI), which is part of the Center for Sustainable Energy at Notre Dame (ND Energy). J.F.D. and D.M.J. thank the Brantley group at the University of Tennessee for access to their laboratory TGA instrument.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/5/4
Y1 - 2020/5/4
N2 - The remarkable resilience of N-heterocyclic carbene (NHC) gold bonds has quickly made NHCs the ligand of choice when functionalizing gold surfaces. Despite rapid progress using deposition from free or CO2-protected NHCs, synthetic challenges hinder the functionalization of NHC surfaces with protic functional groups, such as alcohols and amines, particularly on larger nanoparticles. Here, we synthesize NHC-functionalized gold surfaces from gold(I) NHC complexes and aqueous nanoparticles without the need for additional reagents, enabling otherwise difficult functional groups to be appended to the carbene. The resilience of the NHC−Au bond allows for multi-step post-synthetic modification. Beginning with the nitro-NHC, we form an amine-NHC terminated surface, which further undergoes amide coupling with carboxylic acids. The simplicity of this approach, its compatibility with aqueous nanoparticle solutions, and its ability to yield protic functionality, greatly expands the potential of NHC-functionalized noble metal surfaces.
AB - The remarkable resilience of N-heterocyclic carbene (NHC) gold bonds has quickly made NHCs the ligand of choice when functionalizing gold surfaces. Despite rapid progress using deposition from free or CO2-protected NHCs, synthetic challenges hinder the functionalization of NHC surfaces with protic functional groups, such as alcohols and amines, particularly on larger nanoparticles. Here, we synthesize NHC-functionalized gold surfaces from gold(I) NHC complexes and aqueous nanoparticles without the need for additional reagents, enabling otherwise difficult functional groups to be appended to the carbene. The resilience of the NHC−Au bond allows for multi-step post-synthetic modification. Beginning with the nitro-NHC, we form an amine-NHC terminated surface, which further undergoes amide coupling with carboxylic acids. The simplicity of this approach, its compatibility with aqueous nanoparticle solutions, and its ability to yield protic functionality, greatly expands the potential of NHC-functionalized noble metal surfaces.
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U2 - 10.1002/anie.202001440
DO - 10.1002/anie.202001440
M3 - Article
C2 - 32092219
AN - SCOPUS:85081738959
SN - 1433-7851
VL - 59
SP - 7585
EP - 7590
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 19
ER -