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Title: Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

Abstract

In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a

Authors:
;  [1];  [2];  [3];  [3];  [1];  [3];  [4]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Academy of Science of the Czech Republic, Prague (Czech Republic)
  3. Univ. of Colorado, Boulder, CO (United States)
  4. Univ. of Colorado, Boulder, CO (United States); Academy of Science of the Czech Republic, Prague (Czech Republic)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1255730
Report Number(s):
BNL-112249-2016-JA
Journal ID: ISSN 1089-5639; R&D Project: CO-04; KC0301
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 20; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; exciton transport; triplet; conjugated polymers; molecular wires; exciton diffusion; Laser Electron Accelerator Facility (LEAF)

Citation Formats

Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., and Michl, Josef. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b00648.
Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., & Michl, Josef. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical. United States. doi:10.1021/acs.jpca.6b00648.
Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., and Michl, Josef. Mon . "Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical". United States. doi:10.1021/acs.jpca.6b00648. https://www.osti.gov/servlets/purl/1255730.
@article{osti_1255730,
title = {Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical},
author = {Peter R. Craig and Miller, John R. and Havlas, Zdenek and Trujillo, Marianela and Rempala, Pawel and Kirby, James P. and Noll, Bruce C. and Michl, Josef},
abstractNote = {In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a},
doi = {10.1021/acs.jpca.6b00648},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 20,
volume = 120,
place = {United States},
year = {2016},
month = {5}
}

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Works referencing / citing this record:

CCDC 1508063: Experimental Crystal Structure Determination: EWUSEW : (cyclopentadienyl)-(tetraphenylcyclobutadiene)-nickel(ii) tetrafluoroborate
dataset, October 2016