Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

doi:10.1021/acs.jpca.6b00648

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

Journal Article · Mon May 02 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b00648· OSTI ID:1255730

Miller, John R. ^[1]; Havlas, Zdenek ^[2]; Trujillo, Marianela ^[3]; Rempala, Pawel ^[3]; Kirby, James P. ^[1]; Noll, Bruce C. ^[3]; Michl, Josef ^[4]

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

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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

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Cited by: 2 works

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References (11)

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Magnetic circular dichroism of an unaromatic planar [8]annulene Wen, Jin; Uto, Takayuki; Chalupský, Jakub Journal of Physical Organic Chemistry, Vol. 31, Issue 8 https://doi.org/10.1002/poc.3854	journal	May 2018

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

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