Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Academy of Science of the Czech Republic, Prague (Czech Republic)
- Univ. of Colorado, Boulder, CO (United States)
- Univ. of Colorado, Boulder, CO (United States); Academy of Science of the Czech Republic, Prague (Czech Republic)
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
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0012704
- OSTI ID:
- 1255730
- Report Number(s):
- BNL-112249-2016-JA; R&D Project: CO-04; KC0301
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 20; ISSN 1089-5639
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Magnetic circular dichroism of an unaromatic planar [8]annulene
|
journal | May 2018 |
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