Document Type
Article
Language
eng
Publication Date
2017
Publisher
American Chemical Society
Source Publication
Journal of Physical Chemistry Letters
Source ISSN
1948-7185
Abstract
Understanding geometrical and size dependencies of through-space charge delocalization in multichromophoric systems is critical to model electron transfer and transport in materials and biomolecules. In this work, we examine the size evolution of hole delocalization in van der Waals clusters of fluorene (i.e., (F)n), where a range of geometries are possible, reflecting both π-stacking and C–H/π interactions. Using mass-selected two-color resonant two-photon ionization spectroscopy (2CR2PI), we measure electronic spectra and vertical ionization potentials (IPs) in the gas phase. Results are compared with model covalently linked assemblies (denoted Fn), exhibiting a sterically enforced cofacial (i.e., π-stacked) orientation of chromophores. For both systems, an inverse size dependence (i.e., 1/n) of IP vs cluster size is found. Surprisingly, the values for the two sets fall on the same line! This trend is examined via theory, which emphasizes the important role of π-stacking, and its geometrical dependencies, in the process of hole delocalization in multichromophoric assemblies.
Recommended Citation
Ivanov, Maxim Vadimovich; Reilly, Neil; Uhler, Brandon; Kokkin, Damian; Rathore, Rajendra; and Reid, Scott A., "Cofacially Arrayed Polyfluorenes: Spontaneous Formation of π-Stacked Assemblies in the Gas Phase" (2017). Chemistry Faculty Research and Publications. 913.
https://epublications.marquette.edu/chem_fac/913
Comments
Accepted version. The Journal of Physical Chemistry Letters, Vol. 8, No. 21 (2017): 5272-5276. DOI. © 2017 American Chemical Society. Used with permission.