Oxidative cage opening in the C70 fullerene facilitated by preceding trifluoromethylation.

Two novel derivatives of the C70 fullerene with 9- and 10-membered cage openings were obtained by means of oxidation and decarbonylation of C70(CF3)8. The major product, C70(O)(CF3)8O2, features a cleaved C-C bond transformed into two carbonyl functions plus an ether bridge. The second product, C69O(CF3)8O, has one of the carbonyls replaced with another ether bridge. We provide a DFT analysis of the possible formation pathways to give the oxidized compounds under the action of pyridine N-oxide.

Dissociative Electron Attachment to Hexachlorobenzene.

Gas phase molecules of hexachlorobenzene (C6 Cl6 ) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl- and Cl2- as well as electron detachment (τa ∼250 µs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EAa =1.6-1.9 eV) turns out to be much higher than the quantum-chemical predictions (EAa =0.9-1.0 eV). We discuss the possible reasons behind the observed discrepancy.

E/Z photoisomerization pathway in pristine and fluorinated di(3-furyl)ethenes.

We report an XMCQDPT2 study of the E/Z photoisomerization in a series of fluorinated di(3-furyl)ethenes (3DFEs). Upon excitation, pristine and low-fluorinated 3DFE show conventional behavior of many diarylethenes: unhindered twisting motion toward the pyramidalized zwitterionic state where relaxation to the ground state occurs. However, deep fluorination of 3DFEs can hamper E-to-Z isomerization by giving rise to an alternative excited-state relaxation pathway: an out-of-plane motion of a ring fluorine atom. Importantly, the case of fluorinated 3DFEs reveals serious deficiencies of the popular TDDFT approach. With some commonly used exchange-correlation functionals, the alternative relaxation pathway is not reproduced and, moreover, an irrelevant ring rotation coordinate is predicted instead. Nevertheless, TDDFT remains qualitatively adequate for the E-to-Z twisting coordinate taken alone.

Reversibly switchable methanofullerene by photoexcitation and reduction.

A cyclopropanated derivative of the trifluoromethylated fullerene Cs-C70(CF3)8 demonstrates reversible switching behavior triggered by excited state electron transfer or by negative charging. The switching between the state with connected 62-electron π-system and the state with disjoint 28- and 32-electron conjugated caps is effected by opening/closure of the cyclopropanated bond. A pronounced alteration of the electronic properties upon seemingly minor changes in a large fullerene molecule is an attractive feature for the organic electronic devices where similar fullerene compounds are commonly utilized as electron acceptor materials.

Substitution pattern dependent behavior of the singlet excited states in symmetrically fluorinated biphenyls.

Biphenyls are important basic chromophore systems that offer a possibility to study the effects of chemical substitution on the lower-lying excited states without complications from photoisomerization or other side processes. For several symmetric biphenyls, pristine biphenyl (bP0), 4,4'-difluorobiphenyl (bP2), 2,3,5,6,2',3',5',6'-octafluorobiphenyl (bP8), and perfluorobiphenyl (bP10), we report stationary and ultrafast solution-phase spectra rationalized with the aid of computations by means of the XMCQDPT2 multi-configuration perturbation theory and TDDFT. Polyfluorination tends to broaden the gap between the nearly degenerate S1 + S2 pair of states and the S3 state in bP8 and bP10, yet relaxation from any sheet of the S1-S3 manifold leads through a system of state crossings to the same stationary points in S1. Unlike bP0 and bP2 where the relaxed excited state is planar and non-polar, excited bP8 and bP10 exhibit sudden polarization to give a symmetry-lowered excited state via pseudo-Jahn-Teller interactions involving S1 and S2. Of particular interest is excited bP10 which reveals both sudden polarization and loss of planarity of one phenyl ring. We also demonstrate the unsatisfactory performance of the TDDFT methodology as applied to the biphenyls.

Electrochemically Induced Dimerization of p9mp-C70(CF3)12 Trifluoromethylated Fullerene.

We report a comprehensive study of a novel isomer of C70(CF3)12, p9mp-C70(CF3)12, whose electrochemical behavior differs from most of the other trifluoromethylated fullerenes. The addition pattern of p9mp-C70(CF3)12 is established by means of 19F-19F COSY NMR spectroscopy and DFT calculations. Like p7mp-C70(CF3)10, the new isomer p9mp-C70(CF3)12 undergoes dimerization to the [C70(CF3)12]22- upon single-electron reduction. The electrochemical observations are supported by the DFT calculations of dimerization energy and the temperature dependence of the CW X-band EPR spectroscopy data. Experimentally determined dimerization energies of p9mp-C70(CF3)12-• and p7mp-C70(CF3)10-• in solution are ca -8 and -26 kJ mol-1, respectively, in good correspondence with DFT data.

Chlorination-Promoted Skeletal Transformations of Fullerenes.

Classical fullerenes are built of pentagonal and hexagonal rings, and the conventional syntheses produce only those isomers that obey the isolated-pentagon rule (IPR), where all pentagonal rings are separated from each other by hexagonal rings. Upon exohedral derivatization, the IPR fullerene cages normally retain their connectivity pattern. However, it has been discovered that high-temperature chlorination of fullerenes with SbCl5 or VCl4 can induce skeletal transformations that alter the carbon cage topology, as directly evidenced by single crystal X-ray diffraction studies of the chlorinated products of a series of fullerenes in the broad range of C60 to C102. Two general types of transformations have been identified: (i) the Stone-Wales rearrangement (SWR) that consists of a rotation of a C-C bond by 90°, and (ii) the removal of a C-C bond, i.e., C2 loss (C2L). Single- or multistep SWR and/or C2L transformations afford either classical non-IPR fullerenes bearing fused pentagons (highlighted in red in the TOC picture) or nonclassical (NCx) fullerenes with x = 1-3 heptagonal rings (highlighted in blue in the TOC picture) often flanked by fused pentagons. Several subtypes of the SWR and C2L processes can be further discerned depending on the local topology of the transformed region of the cage. Under the chlorination conditions, the non-IPR and NC carbon cages that would be energetically unfavorable and mostly labile in their pristine state are instantaneously stabilized by chlorination of the pentagon-pentagon junctions and by delimitation of the original spherical π-system into smaller favorable aromatic fragments. The significance of the chlorination-promoted skeletal transformations within the realm of fullerene chemistry is demonstrated by the growing body of examples. To date, these include single- and multistep SWRs in the buckminsterfullerene C60 and in the higher fullerenes C76(1), C78(2), C82(3), and C102(19), single and multistep C2Ls (i.e., cage shrinkage) in C86(16), C88(33), C90(28), C92(50), C96(80), C96(114), and C102(19), and multistep combinations of SWRs and C2Ls in C88(3), C88(33), and C100(18), (IPR isomer numbering in parentheses is according to the spiral algorithm). Remarkably, an IPR precursor can give rise to versatile transformed chlorinated fullerene cages formed via branched pathways. The products can be recovered either in their initial chlorinated form or as more soluble CF3/F derivatives obtained by an additional trifluoromethylation workup. Reconstruction of the skeletal transformation pathways is often complicated due to the lack of the isolable intermediate products in the multistep cases. Therefore, it is usually based on the principle of selecting the shortest pathways between the starting and the final cage. The quantum-chemical calculations illustrate the detailed mechanisms of the SWR and C2L transformations and the thermodynamic driving forces behind them. A particularly important aspect is the interplay between the chlorination patterns and the regiochemistry of the skeletal transformations.

Evaluating the Solvent Stark Effect from Temperature-Dependent Solvatochromic Shifts of Anthracene.

The solvent Stark effect on the spectral shifts of anthracene is studied with temperature-dependent solvatochromic measurements. The Stark contribution ΔvStark to the absorption shift Δvp in polar solvents is measured to be ΔvStark =(53±35) cm-1 , in reasonable agreement with dielectric continuum theory estimate of 28 cm-1 , whereas the major shift Δvp ∼300 cm-1 presumably originates from the solute quadrupole. We pay attention to the accurate correction of Δvp for the nonpolar contribution that is crucial when the shifts are modest in magnitude.

Dissociative Electron Attachment to 2,3,6,7,10,11-Hexabromotriphenylene.

2,3,6,7,10,11-Hexabromotriphenylene (HBTP) and 2,3,6,7,10-pentabromotriphenylene (PBTP) were investigated by means of dissociative electron attachment spectroscopy (DEAS). The dominant decay channel of the transient molecular negative ions consists of elimination of Br- with resonances in the low electron energy region. Formation of long-lived parent anions with autodetachment lifetime τa = 310 µs is observed at thermal electron energies. The adiabatic electron affinities, EAa = 1.12 ± 0.1 eV in HBTP and 1.09 ± 0.1 eV in PBTP, evaluated using a simple Arrhenius approach are in good agreement with those predicted by DFT (XYG3/Def2-TZVPP//PBE0/Def2-TZVPP) calculations.

Experimental and Theoretical Approach to Variable Chlorination-Promoted Skeletal Transformations in Fullerenes: The Case of C102.

The first example of three alternative chlorination-promoted skeletal transformation pathways in the same fullerene cage is presented. Isolated-pentagon-rule (IPR) C102(19) undergoes both Stone-Wales rotations to give non-IPR #283794C102Cl20 and C2 losses to form nonclassical C98 and non-IPR C96. X-ray structural characterization of the transformation products and a theoretical study of their formation pathways are reported.

Rebuilding C60: Chlorination-Promoted Transformations of the Buckminsterfullerene into Pentagon-Fused C60 Derivatives.

In recent years, many higher fullerenes that obey the isolated pentagon rule (IPR) were found capable of rearranging into molecules with adjacent pentagons and even with heptagons via chlorination-promoted skeletal transformations. However, the key fullerene, buckminsterfullerene I h-C60, long seemed insusceptible to such rearrangements. Now we demonstrate that buckminsterfullerene yet can be transformed by chlorination with SbCl5 at 420-440 °C and report X-ray structures for the thus-obtained library of non-IPR derivatives. The most remarkable of them are non-IPR C60Cl24 and C60Cl20 with fundamentally rearranged carbon skeletons featuring, respectively, four and five fused pentagon pairs (FPPs). Further high-temperature trifluoromethylation of the chlorinated mixture afforded additional non-IPR derivatives C60(CF3)10 and C60(CF3)14, both with two FPPs, and a nonclassical C60(CF3)15F with a heptagon, two FPPs, and a fully fused pentagon triple. We discuss the general features of the addition patterns in the new non-IPR compounds and probable pathways of their formation via successive Stone-Wales rearrangements.

Tuning Stilbene Photochemistry by Fluorination: State Reordering Leads to Sudden Polarization near the Franck-Condon Region.

Spontaneous polarization of a nonpolar molecule upon photoexcitation (the sudden polarization effect) earlier discussed for 90°-twisted alkenes is observed and calculated for planar ring-fluorinated stilbenes, trans-2,3,5,6,2',3',5',6'-octofluorostilbene (tF2356) and trans-2,3,4,5,6,2',3',4',5',6'-decafluorostilbene (tF23456). Due to the fluorination, Franck-Condon states S1FC and S2FC are dominated by the quasi-degenerate HOMO-1 → LUMO and HOMO-2 → LUMO excitations, while their interaction gives rise to a symmetry-broken zwitterionic S1 state. After optical excitation of tF2356, one observes an ultrafast (∼0.06 ps) evolution that reflects relaxation from initial nonpolar S3FC to long-lived (1.3 ns in n-hexane and 3.4 ns in acetonitrile) polar S1. The polarity of S1 is evidenced by a solvatochromic shift of its fluorescence band. The experimental results provide a sensitive test for quantum-chemical calculations. In particular, our calculations agree with the experiment, and raise concerns about the applicability of the common TDDFT approach to relatively simple stilbenic systems.

Stepwise Regioselective Hydrogenation of cis-2-C60 (CF2 )2 Homofullerene with [6,6]-Open/Closed Valence Tautomerism.

The homofullerene compound cis-2-C60 (CF2 )2 , which has an unusual kind of open/closed valence tautomerism undergoes consecutive regioselective hydrogenation at bridgehead carbon atoms upon reduction with Zn/Cu couple in H2 O-toluene mixture. The tautomerism barrier in cis-2-C60 (CF2 )2 is negligible in the neutral state, whereas negative charging both impedes tautomeric transformation and promotes regioselective addition of electrophilic species at the bridgehead carbon atoms. In light of this observation, two novel homofullerene derivatives, mixed [6,6]-open/closed C60 (CF2 )2 H2 and [6,6]-open cis-2-C60 (CF2 )2 H4 , were synthesized and their structures were unambiguously determined by means of single crystal X-ray crystallography and NMR spectroscopy.

Trifluoromethyl Derivatives of a Monometallic Cyanide Cluster Fullerene, YCN@C82(6)(CF3)16/18.

Recently discovered monometallic cyanide cluster fullerenes are a novel family of endohedral molecules, whose chemical reactivity has not yet been probed. High-temperature trifluoromethylation of the yttrium cyanide cluster fullerene YCN@C82(6), followed by high-performance liquid chromatography separation and an X-ray diffraction study of the two crystallized fractions, resulted in the structural characterization of YCN@C82(6)(CF3)16/18. In both molecules, exohedrally attached CF3 groups delimit the spherical π system into localized double bonds, benzenoid rings, larger aromatic assemblies, and a conjugated fragment with the only intact pentagon that is involved in coordination to the interior Y atom. We also present theoretical results on charge distributions in the compounds reported.

C100 is Converted into C94 Cl22 by Three Chlorination-Promoted C2 Losses under Formation and Elimination of Cage Heptagons.

Chlorination of the C100 (18) fullerene with a mixture of VCl4 and SbCl5 gives rise to branched skeletal transformations affording non-classical (NC) C94 (NC1)Cl22 with one heptagon in the carbon cage together with the previously reported C96 (NC3)Cl20 with three heptagons. The three-step pathway to C94 (NC1)Cl22 starts with two successive C2 losses of 5:6 CC bonds to give two cage heptagons, whereas the third C2 loss of the 5:5 CC bond from a pentalene fragment eliminates one of the heptagons. Quantum-chemical calculations demonstrate that the two unusual skeletal transformations-creation of a heptagon in C96 (NC3)Cl20 through a Stone-Wales rearrangement and the presently reported elimination of a heptagon through C2 loss-are both characterized by relatively low activation energy.

Anion radicals of isomeric [5,6] and [6,6] benzoadducts of Sc3N@C80: remarkable differences in endohedral cluster spin density and dynamics.

The anion radicals of isomeric [5,6] and [6,6] Sc3N@C80 benzoadducts were studied by electron spin resonance spectroscopy, density functional theory computations, and molecular dynamics. In both compounds the rotation of the Sc3N cluster is frozen and the spin density distribution of the cluster is highly anisotropic, with hyperfine coupling constants of 9.1 and 2 × 33.3 G for the [5,6] adduct and ∼0.6 and 2 × 47.9 G for the [6,6] adduct. Remarkably, the subtle variation of the position of the exohedral group on the surface of the cage results in very pronounced changes in the spin density distribution and the dynamics of the encapsulated Sc3N cluster.

Transalkylation of higher trifluoromethylated fullerenes with C70: a pathway to new addition patterns of C70(CF3)8.

We report three new isomers of C70(CF3)8, structurally related to p(7)mp-C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C70. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY (19)F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p(6),i-C70(CF3)8 in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable.

[6,6]-Open and [6,6]-closed isomers of C70(CF2): synthesis, electrochemical and quantum chemical investigation.

Novel difluoromethylenated [70]fullerene derivatives, C70(CF2 )n (n=1-3), were obtained by the reaction of C70 with sodium difluorochloroacetate. Two major products, isomeric C70(CF2 ) mono-adducts with [6,6]-open and [6,6]-closed configurations, were isolated and their homofullerene and methanofullerene structures were reliably determined by a variety of methods that included X-ray analysis and high-level spectroscopic techniques. The [6,6]-open isomer of C70(CF2 ) constitutes the first homofullerene example of a non-hetero [70]fullerene derivative in which functionalisation involves the most reactive bond in the polar region of the cage. Voltammetric estimation of the electron affinity of the C70(CF2 ) isomers showed that it is substantially higher for the [6,6]-open isomer (the 70-electron π-conjugated system is retained) than the [6,6]-closed form, the latter being similar to the electron affinity of pristine C70. In situ ESR spectroelectrochemical investigation of the C70(CF2 ) radical anions and DFT calculations of the hyperfine coupling constants provide evidence for the first example of an inter-conversion between the [6,6]-closed and [6,6]-open forms of a cage-modified fullerene driven by an electrochemical one-electron transfer. Thus, [6,6]-closed C70(CF2 ) constitutes an interesting example of a redox-switchable fullerene derivative.

Cage shrinkage of fullerene via a C2 loss: from IPR C90(28)Cl24 to nonclassical, heptagon-containing C88Cl22/24.

A new case of chlorination-promoted fullerene cage shrinkage is reported. Chlorination of C90 (isolated pentagon rule isomer no. 28) with VCl4 afforded C88Cl22 with a nonclassic carbon cage (NCC) containing 1 heptagon and 13 pentagons including 2 fused pairs flanking the heptagon. The pathway of C2 abstraction from the C90 cage is suggested on the basis of density functional theory calculations.

Trifluoromethylation of fullerenes: kinetic and thermodynamic control.

We present a survey and theoretical interpretation of the experimental results on trifluoromethylation of fullerenes. A thermodynamic model has been developed to describe the C60/70(CF3)n condensed phase mixtures capable of free exchange of addends and, consequently, of isomerization and changing the degrees of addition. It was found that the purely thermodynamic model affords at least satisfactory prediction of composition of products even for apparently nonequilibrium syntheses. Special cases can be identified by means of detailed kinetic modeling based on the BEP approach, which includes stepwise energetic analysis of the possible trifluoromethylation sequences. This analysis reveals two types of reactions with remarkable difference in rates: direct trifluoromethylation and rearrangements of the CF3 groups. Whenever a particular group of compounds is interrelated through direct addition/abstraction of CF3 groups, it is more or less safe to assume that the said group is in equilibrium describable by the thermodynamic model. In the same time, the slower migration of addends is controlled kinetically, and interference of the sublimation processes frequently prevents its equilibration. Among the most illustrative examples of hindered formation via rearrangements in absence of sufficiently favorable direct trifluoromethylation pathways are certain isomers of the C3v-C60(CF3)18, C70(CF3)18, and C70(CF3)20 compounds.