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Title: Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenes or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [3] ;  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Department; SUNY College at Old Westbury, Old Westbury, NY (United States). Chemistry and Physics Department
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Department
  4. Kyoto Institute of Technology (Japan). Department of Biomolecular Engineering
Publication Date:
Report Number(s):
BNL-112441-2016-JA
Journal ID: ISSN 1932-7447
Grant/Contract Number:
SC0012704; AC02-98CH10886
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 30; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1336067