Effects of Spiroconjugation on the Calculated Singlet−Triplet Energy Gap in 2,2-Dialkoxycyclopentane-1,3-diyls and on the Experimental Electronic Absorption Spectra of Singlet 1,3-Diphenyl Derivatives. Assignment of the Lowest-Energy Electronic Transition of Singlet Cyclopentane-1,3-diyls

• Published in: Journal of the American Chemical Society 2004-01, Vol.126 (2), p.574-582
• Main Authors: Abe, Manabu, Adam, Waldemar, Borden, Weston Thatcher, Hattori, Masanori, Hrovat, David A, Nojima, Masatomo, Nozaki, Koichi, Wirz, Jakob
• Format: Article
• Language: English
• Subjects: Atomic and molecular physics; Exact sciences and technology; Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion); Molecular properties and interactions with photons; Physics; Radiationless transitions, quenching
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja038305b

The effect of a 2,2-ethylene-ketal functionality on the singlet−triplet energy gap (ΔE ST) and on the first electronic transition in singlet cyclopentane-1,3-diyls (1) has been investigated. UDFT calculations predict a significant increase in the preference for a singlet ground state in the diradical with the cyclic ketal at C2 (1g; ΔE ST = −6.6 kcal/mol in C 2 symmetry and −7.6 kcal/mol in C 2 v symmetry), compared to the 2,2-dihydroxy- and 2,2-dimethoxy-disubstituted diradicals (1d, ΔE ST = −3.6 kcal/mol in C 2 symmetry, and 1e, ΔE ST = −3.4 kcal/mol in C 2 symmetry). Spiroconjugation is shown to be responsible for the larger calculated value of |ΔE ST| in 1g, relative to 1d and 1e. A strong correlation between the calculated values of ΔE ST and the computed electronic excitation energies of the singlet diradicals is found for diradicals 1d, 1e, and 1g and for 2,2-difluorocyclopentane-1,3-diyl (1c). A similar correlation between ΔE ST and λcalcd is predicted for the corresponding 1,3-diphenylcyclopentane-1,3-diyls 3, and the predicted blue shift in the spectrum of 3g, relative to 3e, has been confirmed by experimental comparisons of the electronic absorption spectra of the annelated derivatives 2c, 2e, and 2g in a glass at 77 K. The wavelength of the first absorption band in the singlet diradicals decreases in the order 2e (λonset = 650 nm) > 2g (λonset = 590 nm) > 2c (λonset = 580 nm). The combination of these computational and experimental results provides a sound basis for reassignment of the first electronic absorption band in singlet diradicals 2c, 2e, and 2g to the excitation of an electron from the HOMO to the LUMO of these 2,2-disubstituted derivatives of cyclopentane-1,3-diyl.