Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane

Jonathan C. Barnes; Marco Frasconi; Ryan M. Young; Nezar H. Khdary; Wei Guang Liu; Scott M. Dyar; Paul R. McGonigal; Ian C. Gibbs-Hall; Christian S. Diercks; Amy A. Sarjeant; Charlotte L. Stern; William A. Goddard; Michael R. Wasielewski; J. Fraser Stoddart

doi:10.1021/ja505093d

Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane

Jonathan C. Barnes, Marco Frasconi, Ryan M. Young, Nezar H. Khdary, Wei Guang Liu, Scott M. Dyar, Paul R. McGonigal, Ian C. Gibbs-Hall, Christian S. Diercks, Amy A. Sarjeant, Charlotte L. Stern, William A. Goddard, Michael R. Wasielewski, J. Fraser Stoddart^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

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 nm³. 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.

Original language	English (US)
Pages (from-to)	10569-10572
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	30
DOIs	https://doi.org/10.1021/ja505093d
State	Published - Jul 30 2014

Funding

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

Access to Document

10.1021/ja505093d

Cite this

Barnes, J. C., Frasconi, M., Young, R. M., Khdary, N. H., Liu, W. G., Dyar, S. M., McGonigal, P. R., Gibbs-Hall, I. C., Diercks, C. S., Sarjeant, A. A., Stern, C. L., Goddard, W. A., Wasielewski, M. R., & 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. https://doi.org/10.1021/ja505093d

@article{ff6c80c0d03d4e6a8859d3d68bb2043d,

title = "Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane",

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 nm3. 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.",

author = "Barnes, {Jonathan C.} and Marco Frasconi 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.} and Wasielewski, {Michael R.} and Stoddart, {J. Fraser}",

year = "2014",

month = jul,

day = "30",

doi = "10.1021/ja505093d",

language = "English (US)",

volume = "136",

pages = "10569--10572",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "30",

}

Barnes, JC, Frasconi, M, Young, RM, Khdary, NH, Liu, WG, Dyar, SM, McGonigal, PR, Gibbs-Hall, IC, Diercks, CS, Sarjeant, AA, Stern, CL, Goddard, WA, Wasielewski, MR & Stoddart, JF 2014, 'Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane', Journal of the American Chemical Society, vol. 136, no. 30, pp. 10569-10572. https://doi.org/10.1021/ja505093d

TY - JOUR

T1 - Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane

AU - Barnes, Jonathan C.

AU - Frasconi, Marco

AU - Young, Ryan M.

AU - Khdary, Nezar H.

AU - Liu, Wei Guang

AU - Dyar, Scott M.

AU - McGonigal, Paul R.

AU - Gibbs-Hall, Ian C.

AU - Diercks, Christian S.

AU - Sarjeant, Amy A.

AU - Stern, Charlotte L.

AU - Goddard, William A.

AU - Wasielewski, Michael R.

AU - Stoddart, J. Fraser

PY - 2014/7/30

Y1 - 2014/7/30

N2 - 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 nm3. 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.

AB - 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 nm3. 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.

UR - http://www.scopus.com/inward/record.url?scp=84905244957&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84905244957&partnerID=8YFLogxK

U2 - 10.1021/ja505093d

DO - 10.1021/ja505093d

M3 - Article

C2 - 25010450

AN - SCOPUS:84905244957

SN - 0002-7863

VL - 136

SP - 10569

EP - 10572

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 30

ER -

Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 998871: Experimental Crystal Structure Determination

Cite this

Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 998871: Experimental Crystal Structure Determination

Cite this