1,2-dithiin annelated with bicyclo[2.2.2]octene frameworks. One-electron and two-electron oxidations and formation of a novel 2,3,5,6-tetrathiabicyclo[2.2.2]oct-7-ene radical cation with remarkable stability owing to a strong transannular interaction

A stable derivative of 1,2-dithiin annelated with bicyclo[2.2.2]octene frameworks 4 was synthesized as red crystals by the reaction of a dilithiated dimer of bicyclo[2.2.2]octene with elemental sulfur in 59% yield. The cyclic voltammetry of 4 in CH(2)Cl(2) at -78 degrees C showed two reversible oxidation waves at E(1/2) +0.18 V and +0.72 V versus Fc/Fc(+), indicating that the radical cation and dication of 4 are stable under these conditions. Upon chemical one-electron oxidation of 4 in a rather low concentration (4.0 x 10(-4) M) with a 1.5 equiv of SbCl(5) in CH(2)Cl(2), a radical cation 4.+ was formed, whose spin distribution was determined by ESR spectroscopy and by the results of theoretical calculations (UB3LYP/6-31G). The electronic absorption spectrum of 4.+ in CH(2)Cl(2) exhibited a maximum absorption at 428 nm (epsilon = 2.3 x 10(3)), which was hypsochromically shifted from that of neutral 4 (469 nm). When the radical cation 4.+ was produced in higher concentration (0.06 M) in CH(2)Cl(2), a disproportionation was found to take place to give a SbCl(6)(-) salt of remarkably stable radical cation 5.+ having a novel 2,3,5,6-tetrathiabicyclo[2.2.2]oct-7-ene structure. In the X-ray structure of 5.+SbCl(6)(-), the transannular distance (2.794(3) A) between the sulfur atoms was found to be less than the sum of the van der Waals radii of a sulfur atom (3.70 A), suggesting the existence of a bonding interaction between the two disulfide linkages. The theoretical calculations (UB3LYP/6-31G) suggested that this transannular interaction could be described as the resonance between the limiting structures, each of them having a two-center three-electron bond between two sulfur atoms belonging to two different disulfide linkages: thus, both the spin and positive charge are equally delocalized to the four sulfur atoms, causing a great stabilization of 5.+. On the other hand, the 1,2-dithiin radical cation 4.+ was found to readily react with triplet oxygen with subsequent rearrangement to give the 1,2-dithiolium derivative 6+ having a carboxyl group. Finally, the reaction of 4 with an excess amount of SbF(5) gave the corresponding dication 4(2+), which was found to be a 6pi aromatic system on the basis of the results of NMR measurement and theoretical calculations.     

Ion/molecule reactions of isomeric bromobutene radical cations with ammonia

The ion/molecule reaction of the radical cations of three isomeric bromobutenes (2-bromobut-2-ene 1, 1-bromobut-2-ene 2, 4-bromobut-1-ene 3) with ammonia were studied by Fourier transform ion cyclotron resonance spectrometry to reveal the effect of a different position of the bromo substituent relative to the C-C double bond. Further, the reaction pathways of the ion/molecule reactions were analyzed by theoretical calculations at the level B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d). All three bromobutene radical cations 1(.+) to 3(.+) react efficiently with NH(3). The reactions of 1(.+) carrying the halogen substituent at the double bond follow the pattern observed earlier for other ionized vinylic halogenoalkenes. The major reaction corresponds to proton transfer to NH(3) as to be expected from the high acidity of but-2-ene radical cations exposing six acidic H atoms at allylic positions. The other, still important, reaction of 1(.+) is substitution of the Br substituent by NH(3). Although the radical cations 2(.+) and 3(.+) are expected to be as acidic as 1(.+), proton transfer is the minor reaction pathway of these radical cations. Instead, 2(.+) displays bomo substitution as the major reaction. It is suggested that the mechanism of this reaction is analogous to S(N)2' of nucleophilic allylic substitution. Substitution of Br is not efficient for the reactions of 3(.+)-the two major reactions correspond to C-C bond cleavage of the two possible beta-distonic ammonium ions which are generated by the addition of NH(3) to the ionized double bond of 3. This observation, as well as the results obtained for 1(.+) and 2(.+), emphasize the role of the fast and very exothermic addition of a nucleophile to the ionized double bond for the ion/molecule reactions of alkene radical cations. Clearly the energetically-excited distonic ion arising from the addition fragments unimolecularly by energetically accessible pathways. In the case of a halogene subsituent (except F) at the vinylic or allylic position, this is loss of thesubsituent. In the case of remote halogeno substituents, this is C-C bond cleavage adjacent to the radical site of the distonic ion.     

Spherical shape complementarity as an overriding motif in the molecular recognition of noncharged organic guests by p-sulfonatocalix[4]arene: complexation of bicyclic azoalkanes

[reaction: see text] The complexation of p-sulfonatocalix[4]arene (CX4) with 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[3.2.2]non-2-ene (3), 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4), and 1-phenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (5) was studied in D2O at pD 7.4 by 1H NMR spectroscopy. The formation of deep inclusion complexes was indicated by large upfield 1H NMR shifts of the guest protons (up to 2.6 ppm), which were also used to assign, in combination with 2D ROESY spectra, a preferential inclusion of the isopropyl group of 4 and a dominant inclusion of the azo bicyclic residue for 5. The bicyclic azoalkanes 1-3 showed exceptionally high binding constants on the order of 1000 M(-1), 1-2 orders of magnitude larger than for previously investigated noncharged organic guest molecules. The strong binding was attributed to the spherical shape complementarity between the guest and the conical cavity offered by CX4. Interestingly, although the derivatives 4 and 5 are more hydrophobic, they showed a 2-3 times weaker binding, which was again attributed to the deviation from spherical shape in these bridgehead-substituted derivatives. The preferential inclusion of the hydrophilic but spherical bicyclic residue of 5 rather than the hydrophobic aromatic phenyl group provides a unique observation in aqueous host-guest chemistry and corroborates the pronounced spherical shape affinity of CX4.     

Kinetic solvent effects on hydrogen abstraction reactions

Kinetic solvent effects on hydrogen abstractions, namely, acceleration in nonpolar solvents, have been presumed to be restricted to O-H hydrogen donors. We demonstrate that also abstractions from C-H and even Sn-H bonds by cumyloxyl radicals and n,pi*-excited 2,3-diazabicyclo[2.2.2]oct-2-ene are fastest in the gas phase and nonpolar solvents but slowest in acetonitrile. Accordingly, solvent effects on hydrogen abstractions are more general, presumably due to stabilization of the reactive oxygen or nitrogen species in polar solvents.     

Reaction of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene and tert-butoxyl radicals with aryl-substituted benzofuranones

5,7-Di-tert-butyl-3-aryl-3H-benzofuran-2-ones are lactones with potential antioxidant activity, owing to their abstractable benzylic C-H hydrogens. The fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO), an established probe for the hydrogen-donor propensity of chain-breaking antioxidants, was investigated for 16 aryl-substituted benzofuranone derivatives [m,m-(CF3)2, p-CN, m-CN, p-CF3, p-COOCH3, m-CF3, p-Cl, p-F, H, m-CH3, p-CH3, m,p-(CH3)2, p-OCH3, o-CH3, o-CF3, o,m-(CH3)2]. Analysis of the rate data in terms of a linear free energy relationship yielded a reaction constant of rho = +0.35. This implies that n,pi*-excited DBO acts as nucleophilic species. In contrast, hydrogen abstraction of tert-butoxyl radicals from the benzofuranones was accelerated by electron-donating substituents (rho = -0.23), in conformity with the electrophilic character of oxygen-centered alkoxyl radicals. Possible implications for the optimization of the hydrogen-donor propensity of antioxidants through structural variation are discussed.     

Diels-Alder chemistry on alkene functionalized films

A substrate-independent method has been devised for ring formation at solid surfaces. This entails the aminolysis reaction of allylamine with maleic anhydride pulsed plasma polymer films to yield terminal alkene groups at the surface. Subsequent exposure to 1,3-cyclohexadiene leads to a Diels-Alder type (4 + 2) cycloaddition reaction to give a mixture of endo- and exo-bicyclo[2.2.2]oct-2-ene rings.     

A radical-anion chain mechanism initiated by dissociative electron transfer to a bicyclic endoperoxide: insight into the fragmentation chemistry of neutral biradicals and distonic radical anions

The electron-transfer (ET) reduction of two diphenyl-substituted bicyclic endoperoxides was studied in N,N-dimethylformamide by heterogeneous electrochemical techniques. The study provides insight into the structural parameters that affect the reduction mechanism of the O-O bond and dictate the reactivity of distonic radical anions, in addition to evaluating previously unknown thermochemical parameters. Notably, the standard reduction potentials and the bond dissociation energies (BDEs) were evaluated to be -0.55+/-0.15 V and 20+/-3 kcal mol(-1), respectively, the last representing some of the lowest BDEs ever reported. The endoperoxides react by concerted dissociative electron transfer (DET) reduction of the O-O bond yielding a distonic radical-anion intermediate. The reduction of 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (1) results in the quantitative formation of 1,4-diphenylcyclohex-2-ene-cis-1,4-diol by an overall two-electron mechanism. In contrast, ET to 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]octane (2) yields 1,4-diphenylcyclohexane-cis-1,4-diol as the major product; however, in competition with the second ET from the electrode, the distonic radical anion undergoes a beta-scission fragmentation yielding 1,4-diphenyl-1,4-butanedione radical anion and ethylene in a mechanism involving less than one electron. These observations are rationalized by an unprecedented catalytic radical-anion chain mechanism, the first ever reported for a bicyclic endoperoxide. The product ratios and the efficiency of the catalytic mechanism are dependent on the electrode potential and the concentration of weak non-nucleophilic acid. A thermochemical cycle for calculating the driving force for beta-scission fragmentation is presented, and provides insight into why the fragmentation chemistry of distonic radical anions is different from analogous neutral biradicals.     

Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents

The reaction of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene and 2,2-bis(trifluoromethyl)-3,6-dihydro-4,5-dimethyl-2H-thiopyran with i-C₃H₇MgCl leads to the formation of ring opening products as the result of nucleophilic attack of the Grignard reagent on the sulfur atom. According to DFT calculations the reactivity of the sulphur-containing substrate correlates with the strain energy of the heterocycle. The oxidation of 3-thia-4,4-bis(trifluoromethyl)tricyclo[5.2.1.0^2,5]non-7-ene by hydrogen peroxide in hexafluoro-iso-propanol solvent resulted in formation of the corresponding sulfoxide however, the reaction with m-chloroperoxybenzoic acid produced the product of exhaustive oxidation of sulfur and the double bond. In sharp contrast, the oxidation of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene and 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene by MCPBA (2d, 25 °C) proceeds with the preservation of the double bond, leading to the selective formation of the corresponding sulfones.     

Solvent polarity affects H atom abstractions from C-H donors

Kinetic solvent effects on hydrogen abstractions involving C-H donors (dienes, ethers, alkylbenzenes) have been corroborated by experiment and theory (UB3LYP/6-311++G**, polarized continuum model). To single out the effect of solvent polarity, rate constants for scavenging of the cumyloxyl radical and fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene were obtained in binary aprotic mixtures of ethylacetate and acetonitrile. Polar solvents result in a selective stabilization of the reactants (see TOC graphic), which results in slower rate constants.     

Interaction between Exocyclic s-cis-Butadiene and Homoconjugated Functions. Preparation and Diels-Alder Reactivity of Remotely Substituted 2,3-Dimethylidenebicyclo[2.2.2]octanes

The preparations of 5,6-dimethylidene-2exo-bicyclo[2.2.2]octanol ( 8 ), its endo isomer 9 , 5,6-dimethylidene-2-bicyclo[2.2.2]octanone ( 10 ) and 2 exo, 3 exo-epoxy-5,6dimethylidenebicyclo[2.2.2]octane ( 11 ) are described. The kinetics of their cycloaddition to tetracyanoethylene has been measured in toluene at 25° together with those of 2,3-dimethylidenebicyclo[2.2.2]octane ( 7 ) and 5,6-dimethylidenebicyclo[2.2.2]oct-2-ene (12). The effects of remote substitution on the Diels-Alder reactivity of 2,3-dimethyl idenebicyclo[2.2.2]octanes are compared with those observed in the 2,3-dimethylidenenorbornane series ( 1–6 ).     

Analysis of host-assisted guest protonation exemplified for p-sulfonatocalix[4]arene--towards enzyme-mimetic pKa shifts

The pD dependence of the complexation of p-sulfonatocalix[4]arene (CX4) with the azoalkanes 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[2.2.3]non-2-ene (3), and 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4) in D(2)O has been studied. The pD-dependent binding constants, determined by (1)H NMR spectroscopy, were analyzed according to a seven-state model, which included the CX4 tetra- and penta-anions, the protonated and unprotonated forms of the azoalkanes, the corresponding complexes, as well as the complex formed between CX4 and the deuteriated hydronium ion. The variation of the UV absorption spectra, namely the hypsochromic shift in the near-UV band of the azo chromophore upon protonation, was analyzed according to a four-state model. Measurements by independent methods demonstrated that complexation by CX4 shifts the pK(a) values of the guest molecules by around 2 units, thereby establishing a case of host-assisted guest protonation. The pK(a) shift can be translated into improved binding (factor of 100) of the protonated guest relative to its unprotonated form as a result of the cation-receptor properties of CX4. The results are discussed in the context of supramolecular catalytic activity and the pK(a) shifts induced by different types of macrocyclic hosts are compared.     

Tuning aryl, hydrazine radical cation electronic interactions using substituent effects

Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)(*+)) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X)(*+)) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)(*+) and 1- and 2(OMe)(*+). The calculated geometries and optical absorption spectra for 2(Cl)(*+) demonstrate that p-C6H4Cl lies between p-C6H4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the pi*(NN)(+)-centered singly occupied molecular orbital of 2(X)(*+). Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (lambda(v)(sym)) increase in the same order, having values of 1420, 5300, and 6000 cm(-1) for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl pi-centered molecular orbital that interacts with the dinitrogen pi system lies closest in energy to the bonding pi(NN)-centered orbital and has an electronic coupling with it of about 9200 +/- 600 cm(-1), which does not vary regularly with electron donating power of the X substituent.     

Radical Anions of Cyclic Azoalkanes: An ESR,ENDOR, and TRIPLE-Resonance Study

Radical anions often monocyclic and bicyclic azoalkanes containing the azo group in (Z)-conformation, have been fully characterized by their hyperfine data with the use of ESR, ENDOR, and general-TRIPLE-resonance spectroscopy. These azoalkanes are represented by 3,3,5,5-tetramethyl-1-pyrazoline ( 1 ), 2,3-diaza-bicyclo[2.2.1]hept-2-ene ( 4 ), and 2,3-diazabicyclo[2.2.2]oct-2-ene ( 9 ), as well as by their derivatives 2 , 3 , 5 – 8 , and 10 . For all radical anions 1 ″– 10 ″, the ¹⁴N-coupling constant, a_N, is in the range of +0. 83 to +0. 97 mT; this finding indicates that the spin population is essentially restricted to the π system of the azo group. The ¹⁴N-hyperfine anisotropy largely affects the width of ESR lines, particularly at low temperatures. Substantial coupling constants of ⁷Li-, ²³Na-, ³⁹K-, and ¹³³Cs-nuclei point to a close association of the radical anions with their alkali-metal counterions. With the exception of ³⁹K, these nuclei give rise to readily observable ENDOR signals which appear along with those stemming from protons. The prominent hyperfine features of 1 ″– 10 ″ are discussed.     

Corner Bromination of 2-Methyl-endo-tricyclo[3.2.1.0(2,4)]octane and -oct-6-ene

Reaction of 2-methyl-endo-tricyclo[3.2.1.0(2,4)]octane (1) with bromine in CCl(4) gave 2-exo,3-endo-dibromo-2-endo-methylbicyclo[3.2.1]octane (3) which rearranges on silica to 2-exo,6-endo-dibromo-1-methylbicyclo[2.2.2]octane (4). Reaction in methanol gave 4-endo-bromo-2-exo-methoxy-2-endo-methylbicyclo[3.2.1]octane (10) and 4-endo-bromo-2-endo-methoxy-2-exo-methylbicyclo[3.2.1]octane (11) formed by corner attack of the bromine electrophile with C2-C4 bond rupture and inversion of configuration at the site of electrophilic attack. Reaction of 2-methyl-endo-tricyclo[3.2.1.0(2,4)]oct-6-ene (2) with bromine in CCl(4) and methanol gave products of reaction at the alkene site.     

Multiorbital interactions during Acyl radical addition reactions involving imines and electron-rich olefins

Ab initio and DFT calculations reveal that acyl radicals add to imines and electron-rich olefins through simultaneous SOMO --> pi*, pi --> SOMO, and HOMO --> pi*C=O interactions between the radical and the radicalophile. At the CCSD(T)/aug-cc-pVDZ//QCISD/cc-pVDZ level, energy barriers of 15.6 and 17.9 kJ mol(-1) are calculated for the attack of the acetyl radical at the carbon and nitrogen ends of methanimine, respectively. These barriers are 17.1 and 20.4 kJ mol(-1) at BHandHLYP/cc-pVDZ. In comparison, barriers of 34.0 and 23.4 kJ mol(-1) are calculated at BHandHLYP/cc-pVDZ for reaction of the acetyl radical at the 1- and 2-positions in aminoethylene, repectively. Natural bond orbital (NBO) analysis at the BHandHLYP/6-311G** level of theory reveals that SOMO --> pi*imine, pi imine--> SOMO, and LPN --> pi*C=O interactions are worth 90, 278, and 138 kJ mol-1, respectively, in the transition state (2) for reaction of acetyl radical at the nitrogen end of methanimine; similar interactions are observed for the chemistry involving aminoethylene. These multiorbital interactions are responsible for the unusual motion vectors associated with the transition states involved in these reactions. NBO analyses for the remaining systems in this study support the hypothesis that the acetyl radical is ambiphilic in nature.     

Crystal structures of two syn bent tetraalkylhydrazines,their radical cations,and a dication

The crystal structures of 2,7-diazatetracyclo[6.2.2.2^3,6.0^2.7]tetradec-4-ene, 2, its cation radical nitrate salt 2⁺, NO₃^-, 2,7-diazatetracyclo[6.2.2.2^3,6.0^3,7]tetradecane, 3, its dication dihexafluorophosphate salt 3²⁺(PF₆^-)₂, and a low quality structure of the monocation radical tosylate salt of 3 are reported and compared with MNDO calculations of these structures. Cations 2⁺ and 3⁺ are found to be significantly syn bent at nitrogen, and the dication 3²⁺ has a longer N-N distance than its azo analogue, 2,3-diazabicyclo [2.2.2]oct-2-ene (11).     

Spectroscopic and computational studies on the rearrangement of ionized [1.1.1]propellane and some of its valence isomers: the key role of vibronic coupling

The [1.1.1]propellane radical cation 1(?+), generated by radiolytic oxidation of the parent compound in argon and Freon matrices at low temperatures, undergoes a spontaneous rearrangement to form the distonic 1,1-dimethyleneallene (or 2-vinylideneallyl) radical cation 3(?+) consisting of an allyl radical substituted at the 2-position by a vinyl cation. In similar matrix studies, it is found that the isomeric dimethylenecyclopropane radical cation 2(?+) also rearranges to 3(?+). The unusual molecular and electronic structure of 3(?+) has been established by the results of ESR, UV-vis, and IR spectroscopic measurements in conjunction with detailed theoretical calculations. Also of particular interest is an NIR photoinduced reaction by which 3(?+) is cleanly converted to the vinylidenecyclopropane radical cation 4(?+), a process that can be represented in terms of a single electron transfer from the allyl radical to the vinyl cation followed by allyl cation cyclization. The specificity of this photochemical reaction provides additional strong chemical evidence for the structure of 3(?+). Theoretical calculations reveal the decisive role of vibronic coupling in shaping the potential energy surfaces on which the observed ring-opening reactions take place. Thus vibronic interaction in 1(?+) mixes the (2)A(1)' ground state, characterized by its "non-bonding" 3a(1)' SOMO, with the (2)E' first excited state resulting in the destabilization of a lateral C-C bond and the initial formation of the methylenebicyclobutyl radical cation 5(?+). The further rearrangement of 5(?+) to 3(?+) occurs via 2(?+) and proceeds through two additional lateral C-C bond cleavages characterized by transition states of extremely low energy, thereby explaining the absence of identifiable intermediates along the reaction pathway. In these consecutive ring-opening rearrangements, the "non-bonding" bridgehead C-C bond in 1(?+) is conserved and ultimately transformed into a normal bond characterized by a shorter C-C bond length. This work provides strong support for the Heilbronner-Wiberg interpretation of the vibrational structure in the photoelectron spectrum of 1 in terms of vibronic coupling.     

Stereoselectivity of the Diels-Alder additions of exocyclic dienes grafted onto bicyclo[2.2.n]alkanes

The stereoselectivity of the Diels-Alder additions of (norborn-2-eno) [c]furan, (E,E)-5,6-bis(chloromethylene)bicyclo[2.2.2]oct-2-ene, (E,E)-5,6-bis(chloromethylene)-exo-2,3-epoxybicyclo[2.2.2]octane, (E)- and (Z)-2-chloromethylene-3-methylene-exo-5,6-bis(chloromethyl)-7-oxanorbornanes is presented.     

Nature-inspired indolyl-2-azabicyclo[2.2.2]oct-7-ene derivatives as promising agents for the attenuation of withdrawal symptoms: synthesis of 20-desethyl-20-hydroxymethyl-11-demethoxyibogaine

Microwave assisted Diels-Alder cycloaddition of 5-Br-N-benzylpyridinone (2) with methyl acrylate is described to gain an easy access to 7-bromo-2-benzyl-3-oxo-2-aza-5 or 6-carbomethoxy bicyclo[2.2.2]oct-7-enes (3)-(6). The preparation of the ibogaine analogue 20-desethyl-(20-endo)-hydroxymethyl-11-demethoxyibogaine (17) is described by stereoselective hydrogenation of the C(7)-C(8) double bond. Biological evaluation showed an interesting in vitro binding profile toward dopamine transporter, serotonin transporter and opioid receptor systems accompanied by an antiwithdrawal effect in mice for hydroxymethyl 7-indolyl-2-aza-bicyclo[2.2.2]oct-2-ene (14). The simplification of the ibogaine structure appears as a promising approach toward the design of compounds that could reduce the withdrawal symptoms.     

“Inverted” Solvent Effect on Charge Transfer in the Excited State

Faster in cyclohexane than in acetonitrile is the fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by amines and sulfides. Although this photoreaction is induced by charge transfer (CT; see picture) and exciplexes are formed, the increase in the dipole moment of the exciplex is not large enough to offset the solvent stabilization of the excited reactants, and an “inverted” solvent effect results.