Triplet recombination of radical ion pairs: CIDNP effects and DFT calculations on 1,2-dicyanoethylene.

Radical ion pairs generated by electron transfer from photo-excited aromatic hydrocarbons to maleo- and fumaronitrile (cis- and trans-1,2-dicyanoethylene, 1) undergo back electron transfer from singlet and triplet pairs. The pair energies relative to the reactant ground states and to the triplet state, respectively, determine the competition between the recombination pathways. Cross sections through the potential surfaces of the radical anion and the triplet state of 1 have been examined by density functional theory calculations. The radical anion surface has minima in which the carbon and nitrogen skeleton is essentially planar; the central C-C bond is lengthened (weakened), but the barrier to geometric isomerization is still sizeable (31.2 kcal mol(-1)). The triplet energy surface has a minimum at a bisected geometry (plus its enantiomer); rotation of the H-C-CN segments of the triplet yields a syn-periplanar and an anti-periplanar point 9.3 kcal mol(-1) and 8.2 kcal mol(-1) above the minimum, respectively.

Radical cations and triplet states of 1,2-disubstituted cyclopropanes: comparison of potential surfaces.

Radical ion pairs generated by photo-induced electron transfer from 1,2-disubstituted cyclopropanes to various acceptors undergo return electron transfer in pairs of singlet and triplet multiplicity. The pair energies relative to the reactant ground states and to accessible triplet states, respectively, determine the competition between the recombination pathways. The potential surfaces of the radical cations and triplet states of 1,2-diphenyl-, 1, and 1,2-dimethylcyclopropane, 2, have been examined by density functional theory calculations. The radical cation surfaces have minima at geometries that retain significant bonding between C-1 and C-2, preventing geometric isomerization of the radical cations. The triplet potential surfaces are dissociative with minimal rotational differentiation at long distances between C-1 and C-2.

A tribute to Stanislao Cannizzaro, chemical informationist and photochemist.

Stanislao Cannizzaro is known widely for the Cannizzaro reaction, the "disproportionation" of benzaldehyde upon reaction with alkali, for his approach to teaching chemistry, "Sunto di un corso di filosofia chimica", which he presented at the Karlsruhe Congress of 1860, and for his work on the photochemistry of santonin. In Cannizzaro's laboratory two research associates, Giacomo Ciamician and Paul Silber, and a senior colleague, Emanuele Paternó, became acquainted with the basic methods of sunlight-inducd photochemistry.

Biradicals by triplet recombination of radical ion pairs.

Radical ion pairs generated by photoinduced electron transfer may undergo return electron transfer (RET) in pairs of singlet or triplet multiplicity. RET efficiencies are determined by the free energy of RET and the topologies of the potential surfaces of parent molecule, radical ion and triplet state. If radical ion geometries are different from the corresponding triplet states, RET occurs either with cleavage ("dissociative" RET; 1,2-diphenylcyclopropane radical cations) or formation of C-C bonds ("associative" RET; norbornadiene radical cation). Radical ions of some strained ring compounds spontaneously undergo ring-opening; RET to such species form ring-opened triplets without major geometry changes. CIDNP spectroscopy offers unique insights into triplet RET.

Photoinduced electron transfer in ionic liquids: use of 2,4,6-triphenylthiapyrylium as a photosensitizer probe.

The photochemistry of 2,4,6-triphenylthiapyrylium, TPTP+, in an ionic liquid, bmim-PF6, and in zeolite Y has been investigated and compared. Fluorescence spectroscopy was used to characterize the singlet excited state and to demonstrate singlet quenching by dicyclopentadiene, DCP, as an electron donor. Time-resolved laser spectroscopy documents generation of the triplet excited state, 3TPTP+, and reduction by DCP, generating the corresponding radical, TPTP*, and radical ion, DCP+*. The highly polar media stabilize the organic intermediates, causing them to be long lived.

Divergent oxidative rearrangements in solution and in a zeolite: distal vs proximal bond cleavage of methylenecyclopropanes.

Irradiation of 9,10-dicyanoanthracene (DCA) or p-chloranil in the presence of E-1-benzylidene-2-phenylcyclopropane (E-5) in CH(2)Cl(2) causes E-5 to undergo methylenecyclopropane rearrangement. An adduct, Z-7, between DCA and 5 firmly supports the involvement of a bifunctional trimethylenemethane radical cation. In contrast, incorporation of E-5 into HZSM-5 produces trans,trans-1,4-diphenyl-1,3-butadiene radical cation sequestered in the HZSM-5 interior, tt-8(.+)@HZSM-5, identified by ESR and diffuse reflectance spectroscopy. In addition, low yields of tt-8, its cis,trans-isomer (ct-8), and 1-phenyl-1,2-dihydronaphthalene (9) were isolated from the supernatant solution. The sharp contrast between the photoinduced electron-transfer reaction with photosensitizers in solution and the spontaneous reaction with redox-active acidic zeolite offers the prospect of further zeolite-induced regiodivergent reactions in a range of additional substrates.

Incorporation of 2-arylhexa-1,5-diene into pentasil zeolite: A distorted 1-arylcyclohexane-1,4-diyl radical cation at room temperature.

Incorporation into a redox-active pentasil zeolite [(Na,H)-ZSM-5] converted 2-arylhexa-1,5-dienes (9a-c; aryl = phenyl, tolyl, anisyl) into 1-arylcyclohexane-1,4-diyl radical cations, 10a-c*+. The ESR spectra of 10a-c*+ (six lines, g = 2.0026; a = 9.0 G) indicated the presence of five essentially equivalent nuclei, indicating limited delocalization of spin and charge into the phenyl group. Sequestered in the pores of ZSM-5, the three species 10a-c*+ are stable at room temperature, in striking contrast to the parent radical cation in cryogenic matrices: cyclohexane-1,4-diyl radical cation is converted to cyclohexene radical cation above 90 K. The structures of radical cation 10a*+ (X = H) and of the unsubstituted parent were probed by density functional theory (DFT) and ab initio calculations.

Electron Transfer Photochemistry of Homochrysanthemol: Intramolecular Nucleophilic Attack on the Cyclopropane Ring.

The electron-transfer photochemistry of homochrysanthemol, 1, resulted exclusively in intramolecular "substitution" at the quaternary cyclopropane carbon, generating the five-membered cyclic ethers, 2 and 4. The alternative "addition" to the terminal carbon of the double bond, which would result in seven-membered cyclic ethers, 3 and 5, was not observed. Apparently, the five-membered transition state leading to 2 and 4 is significantly favored over the seven-membered one required for formation of 3 and 5. These results stand in interesting contrast to the previously established reaction pattern of chrysanthemol, 8, which is captured exclusively at the terminal vinyl carbon. The divergent regiochemistry of 1(*)(+) and 8(*)(+) (even though the tethers between vinylcyclopropane and alcohol functions differ only by a single CH(2) group) elucidates the principles governing the course of nucleophilic capture in radical cations.

Photoreactions of trans-1-o-Hydroxyphenyl-2-phenylcyclopropane.

The photochemistry of trans-1-o-hydroxyphenyl-2-phenylcyclopropane, trans-1, was studied under a variety of experimental conditions. Direct irradiation through quartz in cyclohexane gave rise mainly to ring-expanded products, 2-phenyl-3,4-dihydro-2H-benzopyran, 2, 2-benzyl-2,3-dihydrobenzofuran, 3, and 1-o-hydroxyphenylindan, 4. The major products, 2 and 3, are rationalized by intramolecular proton transfer. However, a significant fraction of 3 is formed via ring-opening to cinnamylphenol, 5. An additional product, o-(alpha-cyclohexylmethyl)phenol, 7, suggests fragmentation of trans-1 and (formal) insertion of o-hydroxyphenylcarbene into cyclohexane. Direct irradiation in methanol produced methanol adducts 8 and 9 instead of 2, 3, 4, or 7. Finally, acetone-sensitized irradiation of trans-1 resulted in geometric isomerization to cis-1; this result can be rationalized via a biradical intermediate.