Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00461756" target="_blank" >RIV/61388963:_____/16:00461756 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.jpca.6b00648" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.6b00648</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.6b00648" target="_blank" >10.1021/acs.jpca.6b00648</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

Popis výsledku v původním jazyce

Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative la 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 la 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 similar to 0.1 V upon going from 1 to la. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the Supporting Information.

Název v anglickém jazyce

Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

Popis výsledku anglicky

Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative la 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 la 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 similar to 0.1 V upon going from 1 to la. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the Supporting Information.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GBP208%2F12%2FG016" target="_blank" >GBP208/12/G016: Řízení struktury a funkce biomolekul na molekulové úrovni: souhra teorie a experimentu</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

120

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

3456-3462

Kód UT WoS článku

000376841100008

EID výsledku v databázi Scopus

2-s2.0-84973304763