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 language | English (US) |
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Pages (from-to) | 5902-5910 |
Number of pages | 9 |
Journal | Inorganic chemistry |
Volume | 56 |
Issue number | 10 |
DOIs | |
State | Published - 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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CCDC 1552317: Experimental Crystal Structure Determination
Liu, Y. (Creator), Kean, Z. S. (Creator), D'Aquino, A. I. (Contributor), Manraj, Y. D. (Creator), Mendez-Arroyo, J. (Creator) & Mirkin, C. A. (Creator), Cambridge Crystallographic Data Centre, 2017
DOI: 10.5517/ccdc.csd.cc1p39rv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p39rv&sid=DataCite
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CCDC 1552320: Experimental Crystal Structure Determination
Liu, Y. (Creator), Kean, Z. S. (Creator), D'Aquino, A. I. (Contributor), Manraj, Y. D. (Creator), Mendez-Arroyo, J. (Creator) & Mirkin, C. A. (Creator), Cambridge Crystallographic Data Centre, 2017
DOI: 10.5517/ccdc.csd.cc1p39vy, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p39vy&sid=DataCite
Dataset
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CCDC 1552319: Experimental Crystal Structure Determination
Liu, Y. (Creator), Kean, Z. S. (Creator), D'Aquino, A. I. (Contributor), Manraj, Y. D. (Creator), Mendez-Arroyo, J. (Creator) & Mirkin, C. A. (Creator), Cambridge Crystallographic Data Centre, 2017
DOI: 10.5517/ccdc.csd.cc1p39tx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p39tx&sid=DataCite
Dataset