Palladium(II) Weak-Link Approach Complexes Bearing Hemilabile N-Heterocyclic Carbene-Thioether Ligands

Yuan Liu, Zachary S. Kean, Andrea I. D'Aquino, Yashin D. Manraj, Jose Mendez-Arroyo, Chad A. Mirkin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

A new class of homoligated palladium(II) weak-link approach (WLA) complexes bearing hemilabile N-heterocyclic carbene (NHC)-thioether ligands is reported that, unlike previous tweezer-like WLA complexes, expand and contract in a linear fashion when switching between configurational states. These complexes can be chemically switched between a trans open state and a trans closed state via the addition or subsequent extraction of Cl-. These bis(NHC) complexes also display unusual isomerization behavior. For example, an NMR spectroscopic investigation into the solution-state configuration of the open complex reveals the presence of interconverting syn,trans and anti,trans isomers, and a kinetic study shows that the barrier is large enough to isolate, store, and study the anti,trans isomer at room temperature. Notably, the linker length between the NHC and thioether moieties can be tailored with additional -CH2- groups, which affords considerable control over the geometric changes imposed by switching. Therefore, this class of complexes may be useful in the construction of allosterically regulated supramolecular assemblies and materials.

Original languageEnglish (US)
Pages (from-to)5902-5910
Number of pages9
JournalInorganic chemistry
Volume56
Issue number10
DOIs
StatePublished - May 15 2017

Funding

This material is based on work supported by the following awards: U.S. Army Grant W911NF-15-1-0151, National Science Foundation Grant CHE-1149314, and the Vannevar Bush Faculty Fellowship program sponsored by the Basic Research Office of the Assistant Secretary of Defense for Research and Engineering and funded by the Office of Naval Research through Grant N00014-15-1-0043. Z.S.K. acknowledges an International Institute for Nanotechnology postdoctoral fellowship, A.I.d. acknowledges a National Science Foundation graduate research fellowship, and J.M.-A. acknowledges a fellowship from Consejo Nacional de Ciencia y Tecnologia.

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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