CaltechAUTHORS
  A Caltech Library Service

Solid-State Characterization and Photoinduced Intramolecular Electron Transfer in a Nanoconfined Octacationic Homo[2]Catenane

Barnes, Jonathan C. and Frasconi, Marco and Young, Ryan M. and Khdary, Nezar H. and Liu, Wei-Guang and Dyar, Scott M. and McGonigal, Paul R. and Gibbs-Hall, Ian C. and Diercks, Christian S. and Sarjeant, Amy A. and Stern, Charlotte L. and Goddard, William A., III and Wasielewski, Michael R. and Stoddart, J. Fraser (2014) Solid-State Characterization and Photoinduced Intramolecular Electron Transfer in a Nanoconfined Octacationic Homo[2]Catenane. Journal of the American Chemical Society, 136 (30). pp. 10569-10572. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20140829-101214183

[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

713Kb
[img]
Preview
PDF - Supplemental Material
See Usage Policy.

2365Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20140829-101214183

Abstract

An octacationic homo[2]catenane comprised of two mechanically interlocked cyclobis(paraquat-p-phenylene) rings has been obtained from the oxidation of the septacationic monoradical with nitrosonium hexafluoroantimonate. The nanoconfinement of normally repulsive bipyridinium units results in the enforced π-overlap of eight positively charged pyridinium rings in a volume of <1.25 nm^3. In the solid state, the torsional angles around the C–C bonds between the four pairs of pyridinium rings range between 16 and 30°, while the π–π stacking distances between the bipyridinium units are extended for the inside pair and contracted for the pairs on the outside—a consequence of Coulombic repulsion between the inner bipyridinium subunits. In solution, irradiation of the [2]catenane at 275 nm results in electron transfer from one of the paraphenylene rings to the inner bipyridinium dimer, leading to the generation of a temporary mixed-valence state within the rigid and robust homo[2]catenane.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja505093dDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja505093dPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja505093dPublisherSupporting Information
ORCID:
AuthorORCID
Frasconi, Marco0000-0003-2010-175X
Khdary, Nezar H.0000-0001-7130-3402
Liu, Wei-Guang0000-0002-6633-7795
McGonigal, Paul R.0000-0002-8538-7579
Sarjeant, Amy A.0000-0002-1993-0406
Goddard, William A., III0000-0003-0097-5716
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2014 American Chemical Society. Received: May 21, 2014; Published: July 10, 2014. This material is based on work supported by the National Science Foundation (NSF) under CHE-1308107. This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (Project 34-947). The authors would like to thank both KACST and Northwestern University (NU) for their continued support of this research. J.C.B. was supported by a National Defense Science and Engineering Graduate Fellowship from the Department of Defense and gratefully acknowledges support from a Ryan Fellowship awarded under the auspices of the NU International Institute of Nanotechnology (IIN). This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE under grant no. DE-FG02-99ER14999 (M.R.W.). Femtosecond spectroscopy (R.M.Y.) was available as part of the ANSER Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. DE-SC0001059. W.G.L. and W.A.G. thank NSF (CMMI-1120890 and EFRI-1332411) for financial support and to ONR-DURIP and NSF-CSEM for computing resources.
Funders:
Funding AgencyGrant Number
NSFCHE-1308107
King Abdul-Aziz City for Science and Technology (KACST)UNSPECIFIED
Northwestern University34-947
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Department of Energy (DOE)DE-FG02-99ER14999
Department of Energy (DOE)DE-SC0001059
NSFCMMI-1120890
NSFEFMA-1332411
Issue or Number:30
Record Number:CaltechAUTHORS:20140829-101214183
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140829-101214183
Official Citation:Barnes, J. C., Frasconi, M., Young, R. M., Khdary, N. H., Liu, W.-G., Dyar, S. M., . . . Stoddart, J. F. (2014). Solid-State Characterization and Photoinduced Intramolecular Electron Transfer in a Nanoconfined Octacationic Homo[2]Catenane. Journal of the American Chemical Society, 136(30), 10569-10572. doi: 10.1021/ja505093d
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:49061
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:29 Aug 2014 19:49
Last Modified:03 Oct 2019 07:10

Repository Staff Only: item control page