Electronic Communication between S=1/2 Spins in Negatively‐charged Double‐caged Fullerene C60 Derivative Bonded by Two Single Bonds and Pyrrolizidine Bridge

Radical anion salt {cryptand[2.2.2] (K⁺)}₂(bispheroid)^2??3.5C₆H₄Cl₂ ( 1 ) of the double‐caged fullerene C₆₀ derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)^2? dianions with two interacting S=1/2 spins on the neighboring cages. Low‐temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/k_B=?78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/k_B=?44.7 K) in previously studied (C₆₀^?)₂ dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum‐chemical calculations of the lowest electronic state of the dianions by means of multi‐configuration quasi‐degenerate perturbation theory support the experimental findings.     

Structure,Optical, and Magnetic Properties of (PPN+)2(C702−)⋅2 C6H4Cl2, which Contains Dianionic Polymeric (C702−)n Chains

A new salt, (PPN⁺)₂(C₇₀^2?) ? 2 C₆H₄Cl₂ ( 1 ), which contains C₇₀^2? dianions, has been obtained as single crystals (PPN⁺=bis(triphenylphosphine)iminium cation). The C₇₀^2? dianions form polymeric zigzag (C₇₀^2?)_n chains, in which the fullerene units are bonded through single C? C bonds of length 1.581(5)–1.586(6) Å. The distance between the centers of neighboring C₇₀^2? units is 10.441 Å. The optical and magnetic properties of (C₇₀^2?)_n have also been studied. Decreasing the symmetry of C₇₀ in the polymer activate about 20 new IR bands in addition to the 10 IR‐active bands of the starting C₇₀. The polymeric structure shows absorptions in the visible and NIR regions, with three main bands at 890, 1200, and 1550 nm, instead of one band of isolated C₇₀^2? dianions at 1165–1184 nm. We concluded that the (C₇₀^2?)_n polymer was diamagnetic, with a negative molar magnetic susceptibility of ?3.82×10^?4 emu mol^?1 per C₇₀^2? dianion. The polymer is EPR silent and a weak narrow EPR signal in salt 1 is due to impurities, which only constitute 0.84 % of spin S=1/2 of the total amount of fullerene C₇₀.     

Cationic Complexes of Hydrogen with Helium

High‐resolution mass spectra of helium nanodroplets doped with hydrogen or deuterium reveal that copious amounts of helium can be bound to H⁺, H₂⁺, H₃⁺, and larger hydrogen‐cluster ions. All conceivable He_nH_x⁺ stoichiometries are identified if their mass is below the limit of ≈120 u set by the resolution of the spectrometer. Anomalies in the ion yields of He_nH_x⁺ for x=1, 2, or 3, and n≤30 reveal particularly stable cluster ions. Our results for He_nH₁⁺ are consistent with conclusions drawn from previous experimental and theoretical studies which were limited to smaller cluster ions. The He_nH₃⁺ series exhibits a pronounced anomaly at n=12 which was outside the reliable range of earlier experiments. Contrary to findings reported for other diatomic dopant molecules, the monomer ion (i.e. H₂⁺) retains helium with much greater efficiency than hydrogen‐cluster ions.     

Electron‐Driven Self‐Assembly of Salt Nanocrystals in Liquid Helium

The self‐assembly of salt nanocrystals from chemical reactions inside liquid helium is reported for the first time. Reaction is initiated by an electron impacting a helium nanodroplet containing sodium atoms and SF₆ molecules, leading to preferential production of energetically favorable structures based on the unit cell of crystalline NaF. These favorable structures are observed as magic number ions (anomalously intense peaks) in mass spectra and are seen in both cationic and anionic channels in mass spectra, for example, (NaF)_nNa⁺ and (NaF)_nF^?. In the case of anions the self‐assembly is not directly initiated by electrons: the dominant process involves resonant electron‐induced production of metastable electronically excited He^? anions, which then initiate anionic chemistry by electron transfer.     

Synthesis,Structure, and Properties of the Fullerene C60 Salt of Crystal Violet, (CV+)(C60.−)⋅0.5 C6H4Cl2, which Contained Closely Packed Zigzagged C60.− Chains

The reduction of fullerene C₆₀ by zinc dust in the presence of crystal violet cations (CV⁺) yielded a deep‐blue solution, from which crystals of (CV⁺)(C₆₀^.?) ? 0.5 C₆H₄Cl₂ ( 1 ) were obtained by slow mixing with n‐hexane. The salt contained isolated, closely packed zigzagged chains that were composed of C₆₀^.? radical anions with a uniform interfullerene center‐to‐center distance of 9.98 Å. In spite of the close proximity of the fullerenes, they did not dimerize, owing to spatial separation by the phenyl substituents of CV⁺. The room‐temperature conductivity of compound 1 was 3×10^?2 S cm^?1 along the fullerene chains. The salt exhibited semiconducting behavior, with an activation energy of E_a=167 meV. Spins localized on C₆₀^.? were antiferromagnetically coupled within the fullerene chains, with a Weiss temperature of ?19 K without long‐range magnetic ordering down to 1.9 K.     

High‐Potential Perfluorinated Phthalocyanine–Fullerene Dyads for Generation of High‐Energy Charge‐Separated States: Formation and Photoinduced Electron‐Transfer Studies

High oxidation potential perfluorinated zinc phthalocyanines (ZnF_nPcs) are synthesised and their spectroscopic, redox, and light‐induced electron‐transfer properties investigated systematically by forming donor–acceptor dyads through metal–ligand axial coordination of fullerene (C₆₀) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine‐ (Py) and phenylimidazole‐functionalised fullerene (C₆₀Im) derivatives to the zinc centre of the F_nPcs. The determined binding constants, K, in o‐dichlorobenzene for the 1:1 complexes are in the order of 10⁴ to 10⁵ M ^?1; nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6‐31G* method. The HOMO and LUMO levels are located on the Pc and C₆₀ entities, respectively; this suggests the formation of ZnF_nPc^.+–C₆₀Im^.? and ZnF_nPc^.+–C₆₀Py^.? (n=0, 8 or 16) intra‐supramolecular charge‐separated states during electron transfer. Electrochemical studies on the ZnPc–C₆₀ dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge‐separated states. The energy of the charge‐separated state for dyads composed of ZnF_nPc is higher than that of normal ZnPc–C₆₀ dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar‐energy harvesting and optoelectronic device building applications.     

Energetics and Structures of Charged Helium Clusters: Comparing Stabilities of Dimer and Trimer Cationic Cores

We present accurate ab initio calculations of the most stable structures of He_n⁺ clusters in order to determine the more likely ionic core arrangements existing after reaching structural equilibrium of the clusters. Two potential energy surfaces are presented: one for the He₂⁺ and the other with the He₃⁺ linear ion, both interacting with one He atom. The two computed potentials are in turn employed within a classical structure optimization where the overall interaction forces are obtained within the sum‐of‐ potentials approximation described in the main text. Because of the presence of many‐body effects within the ionic core, we find that the arrangements with He₃⁺ as a core turn out to be energetically preferred, leading to the formation of He₃⁺(He)_n?3 stable aggregates. Nanoscopic considerations about the relative stability of clusters with the two different cores are shown to give us new information on the dynamical processes observed in the impact ionization experiments of pure helium clusters and the importance of pre‐equilibrium evaporation of the ionic dimers in the ionized clusters.     

Facile Separation,Spectroscopic Identification,and Electrochemical Properties of Higher Trifluoromethylated Derivatives of [70]Fullerene

We survey the structure and electronic properties of the family of higher trifluoromethylated C₇₀(CF₃)_n molecules with n=14, 16, 18, and 20. Twenty‐two available compounds, of which thirteen are newly obtained and characterized, demonstrate the broad diversity of π‐system topologies, which enabled us to study the interplay between the CF₃ addition pattern and the electronic properties. UV/Vis spectroscopic and cyclic voltammetric studies demonstrate the importance of the exact addition pattern rather than the plain number of addends. Of particular interest is the skew pentagonal pyramid (SPP) addition pattern, which enables formation of closed‐shell cyclopentadienyl anions C₇₀(CF₃)_{n? 1} ^? through CF₃ detachment upon electron transfer. A detailed study of the process is presented for a SPP‐C₇₀(CF₃)₁₆ where potentiostatic electrolysis at the second reduction potential gives C₇₀(CF₃)₁₅^? oxidizable to a persistent C₇₀(CF₃)₁₅^· radical. Together with the literature data for the lower C₇₀(CF₃)_n compounds with n=2–12, the present results show good correlation between the experimental boundary level positions and the DFT predictions. The compounds turn out to be electron acceptor molecular semiconductors with experimental LUMO energies and HOMO–LUMO gaps within the ranges of ?4.3 to ?3.7 eV and 1.6 to 3.3 eV, respectively, depending on the shape of the conjugated fragments. The HOMO levels fall within the range of ?5.6 to ?6.9 eV and show linear correlation with the number of addends.     

Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C60 and Triphenylamine–Corrole‐C60 Donor–Acceptor Conjugates

Closely positioned donor–acceptor pairs facilitate electron‐ and energy‐transfer events, relevant to light energy conversion. Here, a triad system TPACor‐C₆₀ , possessing a free‐base corrole as central unit that linked the energy donor triphenylamine ( TPA ) at the meso position and an electron acceptor fullerene (C₆₀) at the β‐pyrrole position was newly synthesized, as were the component dyads TPA‐Cor and Cor‐C₆₀ . Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady‐state fluorescence studies showed efficient energy transfer from ¹ TPA* to the corrole and subsequent electron transfer from ¹corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron‐transfer products, the corrole radical cation ( Cor^?+ in Cor‐C₆₀ and TPA‐Cor^?+ in TPACor‐C₆₀ ) and fullerene radical anion (C₆₀^??), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, k_CS, was found to be about 10¹¹ s^?1, suggesting the occurrence of an ultrafast charge‐separation process. Interestingly, although an order of magnitude slower than k_CS, the rate of charge recombination, k_CR, was also found to be rapid (k_CR≈10¹⁰ s^?1), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge‐separated species relaxed directly to the ground state in polar solvents while in toluene, formation of ³corrole* was observed, thus implying that the energy of the charge‐separated state in a nonpolar solvent is higher than the energy of ³corrole* being about 1.52 eV. That is, ultrafast formation of a high‐energy charge‐separated state in toluene has been achieved in these closely spaced corrole–fullerene donor–acceptor conjugates.     

Synthesis and structure analysis of (K[DB18 C6])4(C60)5·12THF containing C60 in three different bonding states

A new fulleride, (K[DB18C6])₄(C₆₀)₅?12 THF, was prepared in solution using the “break‐and‐seal” approach by reacting potassium, fullerene, and dibenzo[18]crown‐6 in tetrahydrofuran. Single crystals were grown from solution by the modified “temperature difference method”. X‐ray analysis was performed revealing a reversible phase transition occurring on cooling. Three different crystal structures of the title compound at different temperatures of data acquisition are addressed in detail: the “high‐temperature phase” at 225 K (C2, Z=2, a=49.055(1), b=15.075(3), c=18.312(4) Å, β=97.89(3)°), the “transitional phase” at 175 K (C2 m, Z=2, a=48.436(5), b=15.128(1), c=18.280(2) Å, β=97.90(1)°), and the “low‐temperature phase” at 125 K (Cc, Z=4, a=56.239(1), b=15.112(3), c=36.425(7) Å, β=121.99(1)°). On cooling, partial radical recombination of C₆₀^.? into the (C₆₀)₂^2? dimeric dianion occurs; this is first time that the fully ordered dimer has been observed. Further cooling leads to formation of a superstructure with doubled cell volume in a different space group. Below 125 K, C₆₀ exists in the structure in three different bonding states: in the form of C₆₀^.? radical ions, (C₆₀)₂^2? dianions, and neutral C₆₀, this being without precedent in the fullerene chemistry, as well. Experimental observations of one conformation exclusively of the fullerene dimer in the crystal structure are further explained on the basis of DFT calculations considering charge distribution patterns. Temperature‐dependent measurements of magnetic susceptibility at different magnetic fields confirm the phase transition occurring at about 220 K as observed crystallographically, and enable for unambiguous charge assignment to the different C₆₀ species in the title fulleride.     

Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me₂NCH₂F to the electron‐deficient phosphanes (C₂F₅)_nPF_3?n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C₂F₅)_nF_5?nP(CH₂NMe₂?CH₂NMe₂)] are converted into the corresponding phosphonium salts [(Me₃PCH₂NMe₂]⁺[(C₂F₅)_nF_5?nP(CH₂NMe₂)]^? by treatment with PMe₃. In addition [(C₂F₅)₃F₂P(CH₂NMe₂?CH₂NMe₂)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF₃ analogue. Reaction of [(C₂F₅)₃F₂P(CH₂NMe?CH₂NMe₃)] and PMe₃ gave rise to the formation of the zwitterionic phosphonium phosphate [(C₂F₅)₃F₂P(CH₂NMe?CH₂PMe₃)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs⁺[(C₂F₅)₃F₂P(CH₂NMe₂)]^? was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.     

Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets

The synthesis of a stereochemically pure concave tribenzotriquinacene receptor ( 7 ) for C₆₀ fullerene, possessing C₃ point group symmetry, by threefold condensation of C₂‐symmetric 1,2‐diketone synthons ( 5 ) and a hexaaminotribenzotriquinacene core ( 6 ) is described. The chiral diketone was synthesized in a five‐step reaction sequence starting from C_2h‐symmetric 2,6‐di‐tert‐butylanthracene. The highly diastereo‐discriminating Diels–Alder reaction of 2,6‐di‐tert‐butylanthracene with fumaric acid di(?)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by ¹H and ¹³C NMR spectroscopy, mass spectrometry and single crystal X‐ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7 % ee, based on the ee (99.9 %) of the chiral synthon ( 1 ). The absolute configuration of 7 could thus be established as all‐S [(2S,7S,16S,21S,30S,35S)‐( 7 )]. Spectroscopic titration experiments reveal that the host forms 1:1 complexes with either pure fullerene (C₆₀) or fullerene derivatives, such as rotor 1′‐(4‐nitrophenyl)‐3′‐(4‐N,N‐dimethylaminophenyl)‐pyrazolino[4′,5′:1,2][60]fullerene ( R ). The complex stability constants of the complexes dissolved in CHCl₃/CS₂ (1:1 vol. %) are K([ C₆₀ ? 7 ])=319(±156) M ^?1 and K([ R ? 7 ])=110(±50) M ^?1. With molecular dynamics simulations using a first‐principles parameterized force field the asymmetry of the rotational potential for [ R ? 7 ] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.     

[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.     

Role of Helium Droplets in Mass Spectra of Diatomics: Suppression of Dissociative Reactions

It is generally accepted that electron impact of doped helium nanodroplets initially produces a positively charged helium atom, which then ionizes the dopant if the two come into contact. In effect the He⁺ can initiate ion-molecule reactions. However, the effect of the surrounding helium on ion-molecule reactions remains ambiguous. To explore this, electron-induced chemistry has been investigated for the diatomic molecules O₂, CO and N₂. The helium is found to significantly suppress dissociative ion product channels.     

Photovoltaic Characteristics of a Naphthylamine Derivative

Organic photovoltaic （OPV） cells were fabricated via vacuum vapor deposition with {4-[2-（3-di-cyanomethylidene-5,5-dimethylcyclohexenyl）vinyl]phenyl}di（1-naphthyl）amine （DNP-2CN） as the electron donor, and fullerene （C60） as the electron acceptor. A thin film （10 nm） of tris（8-quinolinolato）aluminum （Alq3） was adopted as the buffer layer. A device based on this DNP-2CN exhibited an open circuit voltage （Voc） of 370 mV, a short-circuit current density （Jsc） of 0.61 mAocm 2, and a white-light power conversion efficiency （ η） of 0.09% （AM1.5, 75 mW.cm^- 2）.     

Synthesis,characterization and theoretical and fluorescence emission microscopy studies of new Pd/Pt–cyclopropa[60]fullerene complexes: Application of Taguchi method for optimization of parameters in Suzuki–Miyaura reaction

The reactions of unsymmetric phosphorus ylides of the type [Ph₂P(CH₂)_nPPh₂?C(H)C(O)C₆H₄‐p‐CN] (n = 1 (Y¹); n = 2 (Y²)) with C₆₀ and M(dba)₂ (M = Pd or Pt; dba = dibenzylideneacetone) are reported. Based on the various coordination modes of these ylides in complexation, the following new Pd/Pt–cyclopropa[60]fullerene complexes were obtained: P,C‐coordinated [(η²‐C₆₀)Pd(κ²‐Y¹)] ( 1 ) and [(η²‐C₆₀)Pt(κ²‐Y¹)] ( 2 ) complexes and P‐coordinated [(η²‐C₆₀)Pd(Y²)₂] ( 3 ) and [(η²‐C₆₀)Pt(Y²)₂] ( 4 ) complexes. These compounds were characterized using Fourier transform infrared, UV–visible and NMR (¹H, ¹³C and ³¹P) spectroscopies and scanning electron microscopy. Furthermore, cytotoxicity studies showed that nanoparticles of these complexes can be used as non‐toxic labels for cellular imaging application. Also energy decomposition analysis results revealed that the percentage contribution of ΔE_elec in total interaction energy is considerably larger than that of ΔE_orb. Thus, in all complexes the (η²‐C₆₀)M? (Y¹) bond is considerably more electrostatic in nature than the (η²‐C₆₀)? M(Y¹) bond. Finally, by application of the Taguchi method for optimization of parameters in Suzuki–Miyaura reaction, the catalytic activity of Pd complexes 1 and 3 was investigated in the cross‐coupling reaction of various aryl chlorides with phenylboronic acid. According to analysis of variance results, solvent has the highest F value and it has high contribution percentage (36.75%) to the yield of Suzuki–Miyaura reaction.     

Substituent‐Stabilized Organic Dianions in the Gas Phase and Their Potential Use as Electrolytes in Lithium‐Ion Batteries

Using density functional theory and a hybrid exchange‐correlation functional, a systematic study of the stability and electronic structure of neutral and multiply charged organic molecules, B_nC_6?nX₆ (n=0, 1, 2; X=H, F, CN) and B_nC_5?nX₅ (n=0, 1; X=H, F, CN) is performed. The results show that in addition to the aromaticity of the molecules, substituents play an important role in stabilizing the organic dianion complexes. In particular, it is demonstrated that CN groups are responsible for the stability of organic dianions as it has recently been found to be the case in B‐cage compounds such as B₁₂(CN)₁₂^2? and CB₁₁(CN)₁₂^2?. It is also shown that the stable organic dianions B₂C₄(CN)₆^2? and BC₄(CN)₅^2? might be halogen‐free electrolytes in Li‐ion batteries.     

Regioselective Sequential Additions of Nucleophiles and Electrophiles to Perfluoroalkylfullerenes: Which Cage C Atoms Are the Most Reactive and Why?

The sequential addition of CN^? or CH₃^? and electrophiles to three perfluoroalkylfullerenes (PFAFs), C_s‐C₇₀(CF₃)₈, C₁‐C₇₀(CF₃)₁₀, and C_s‐p‐C₆₀(CF₃)₂, was carried out to determine the most reactive individual fullerene C atoms (as opposed to the most reactive C?C bonds, which has previously been studied). Each PFAF reacted with CH₃^? or CN^? to generate metastable PFAF(CN)^? or PFAF(CH₃)₂^2? species with high regioselectivity (i.e., one or two predominant isomers). They were treated with electrophiles E⁺ to generate PFAF(CN)(E) or PFAF(CH₃)₂(E)₂ derivatives, also with high regioselectivity (E⁺=CN⁺, CH₃⁺, or H⁺). All of the predominant products, characterized by mass spectrometry and ¹⁹F NMR spectroscopy, are new compounds. Some could be purified by HPLC to give single isomers. Two of them, C₇₀(CF₃)₈(CN)₂ and C₇₀(CF₃)₁₀(CH₃)₂(CN)₂, were characterized by single‐crystal X‐ray diffraction. DFT calculations were used to propose whether a particular reaction is under kinetic or thermodynamic control.