Solvent-Dependent C−OH Homolysis and Heterolysis in Electronically Excited 9-Fluorenol: The Life and Solvation Time of the 9-Fluorenyl Cation in Water

• Published in: Chemistry : a European journal Vol. 7; no. 8; pp. 1808 - 1815
• Main Authors: Gurzadyan, Gagik G., Steenken, Steen
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 17.04.2001; WILEY‐VCH Verlag GmbH
• Subjects: carbocations; fluorene; photodissociation; picosecond spectroscopy; solvent effects
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/1521-3765(20010417)7:8<1808::AID-CHEM18080>3.0.CO;2-8

The primary pathways of the photodecomposition of 9‐fluorenol (FOH) were studied in polar and nonpolar solvents by use of laser flash‐photolysis with a resolution time of 10 ps. In solvents of high polarity, that is, in 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP), 2,2,2‐trifluoroethanol (TFE), formamide or water, the fluorenyl cation, F+, forms by heterolytic C−O bond cleavage. In H2O, the initial (10 ps) spectrum of F+ has λmax at <460 nm. This absorption red‐shifts with τ=25 ps to the “classical” spectrum with λmax=510–515 nm. This process is assigned to the solvation of the initial “naked” cation, or rather, the contact ion pair. The lifetime of the solvated fluorenyl cation in H2O (or D2O) and TFE was measured to be τ=20 ps and 1 ns, respectively. In solvents of lower polarity such as alkanes, ethers and alcohols, the long‐lived (τ1/2 ≈1 μs) fluorenyl radical, F., (λmax=500 nm) forms through homolytic C−O cleavage. In addition to the radical and the cation, the vibrationally relaxed excited singlet state of FOH is seen with its absorption at ≈640 nm; its lifetime is strongly dependent on the solvent, from 10 ps for formamide to 1.7 ns for cyclohexane. The rate constant for singlet decay increases exponentially with the polarity of the solvent (as expressed by the Dimroth–Reichardt ET value) or with the Gutmann solvent acceptor number. The relaxation of S1 to S0 is accompanied by homolytic C9−O bond cleavage (except in HFIP, TFE, and water, where S1 is not seen). The primary pathways of the photodecomposition of 9‐fluorenol (FOH) were studied in polar and nonpolar solvents by use of ps laser flash‐photolysis. The solvent‐dependence of homo‐ and heterolytic bond cleavage is presented (see scheme, E = O, N).