Intramolecular electronic interactions between nonconjugated arene and quinone chromophores.
The novel surprisingly colorful dark blue and orange-red molecular clips 1 and 2 containing a central p-benzoquinone spacer-unit and anthracene or napththalene sidewalls were synthesized by DDQ oxidation of the corresponding colorless hydroquinone clips 7 and 8. The colors of the quinone clips result from broad absorption bands in the visible range (1, lambda(max) = 537 nm and 2, lambda(max) = 423 and lambda(shoulder) =515 nm) showing bathochromic shifts of 112 and 90 nm, respectively, compared to the similarly tetraalkyl-substituted duroquinone 31, even though the clips 1 and 2 only contain insulated pi systems as chromophores, a central tetraalkyl-substituted p-benzoquinone spacer-unit and two anthracene or two naphthalene sidewalls. To elucidate the electronic properties of these clips, we prepared the compound 3, the anti-configured isomer of clip 2, and the benzene-, naphthalene-, and anthracene-substituted quinones 4, 5, and 6, the so-called "half-clips". The "half-clips" 6 and 5 show a similar color change and the same trend in the UV/vis absorption spectra as the anthracene and naphthalene clip 1 and 2. This finding already rules out that the color of these systems is a result of "through-space" pi-pi interactions between the aromatic sidewalls in the molecular clips 1 and 2. Quantum chemical ab initio calculations provide good evidence that the bathochromic shift of the absorption band at the longest wavelength observed in the UV/vis spectra of the clip quinones 2, 3, and 1 and the "half-clip" quinones 4, 5, and 6 with an increasing number of rings in the anellated aromatic unit (from benzene to anthracene) is the result of an increasing configuration interaction between a n --> pi* excitation of the quinoid component and a pi --> pi* excitation with intramolecular charge transfer (CT) character. The initial pi orbitals involved here and in higher lying transitions mainly stem from through-space interactions between pi orbitals of the aromatic sidewalls and pi orbitals of the quinone moiety with varying degree of mixing. The configuration interaction in the excited states can be considered to be a homoconjugation, that is, the relevant charge transfer states are formed across an allegedly insulating aliphatic bridge. The UV/vis spectra of the molecular clips 1-3, the "half-clips" 4-6, and the quinones 32 and 33 simulated by means of quantum chemical ab initio calculations agree well with the experimental spectra.
Institut für Organische Chemie and Institut für Anorganische Chemie, Universität Duisburg-Essen, 45117 Essen, Germany. georg.jansen@uni-duisburg-essen.de
Georg
G
Jansen
Björn
B
Kahlert
Frank-Gerrit
FG
Klärner
Roland
R
Boese
Dieter
D
Bläser
D000873:Anthracenes / Q000737:chemistry; D016227:Benzoquinones / Q000737:chemistry*; D003116:Color; D004583:Electrons; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
D000873:Anthracenes; D016227:Benzoquinones; D006841:Hydrocarbons, Aromatic; D009281:Naphthalenes; C031721:naphthalene; C004532:quinone; C034020:anthracene