Fulvalene‐Embedded Perylene Diimide and Its Stable Radical Anion

The first example of a two‐state (neutral and reduced), stable electron‐accepting material and its radical anion is presented. FV‐PDI, generated from cyclocarbonylation and then a carbonyl coupling reaction, shows a largely degenerate LUMO of ?4.38 eV based on the delocalization of π‐electrons across the whole molecular skeleton through a fulvalene bridge. The stability and electron affinity allow spontaneous electron transfer to afford a stable radical anion. Spectroscopic characterization and structural elucidation showed that the radical anion [FV‐PDI]^.? has remarkable stability and near‐infrared absorptions extending to 1200 nm. Single‐crystal X‐ray diffraction analyses revealed significant changes in the molecular shape and packing arrangement of the formed radical anion. The central C?C bond linking the two PDI halves is lengthened from approximately 1.33 to 1.43 Å, and the alternating arrangement of positively and negatively charged units favor the stable charge‐transfer complex.     

Evidence of AlII Radical Addition to Benzene

Electrophilic Al^III species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low-valent Al^I aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an Al^II radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC₈ in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa-1,3(orl,4)-dienes as Birch-type reduction product. X-ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable Al^II radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.     

The Triply Deprotonated Acetonitrile Anion CCN3− Stabilized in a Solid

The unprecedented, fully deprotonated form of acetonitrile, the acetonitriletriide anion CCN³⁻, is experimentally realized for the first time in the stabilizing bulk host framework of the Ba₅[TaN₄][C₂N] nitridometalate via a one‐pot synthesis from the elements under moderate conditions (920 K). The molecular structure of this long‐sought acetonitrile derivative is confirmed by X‐ray diffraction, as well as NMR, IR, and Raman spectroscopy. The anion is isoelectronic to the CO₂ molecule, and, in contrast to acetonitrile (H₃C−C≡N), the electron pairs are shifted towards two double bonds, that is, [C=C=N]³⁻.     

New bifunctional initiator for use in anionic polymerizations

The synthesis is described of narrow distribution polystyrenes initiated by the 2,7-dimethyl-3,6-diphenyl-octane dianion (DDO²⁻). DDO²⁻ was synthesized via electron transfer from lithium or potassium metal to 3-methyl-2-phenyl-1-butene (MPB) in tetrahydrofuran at temperatures between −78 and −100 °C. In contrast to the analogous α-methyl styrene, there was no evidence of MPB polymerization. The structure of DDO²⁻ was demonstrated by ¹H and ¹³C NMR, as well as gas chromatography/mass spectrometry characterization of the DDO²⁻ protonation and methylation products. In addition, kinetic studies were performed by ultraviolet–visible spectrophotometry for the determination of the stability of this anion in comparison with other similar species. The initiation of styrene by DDO²⁻ led to narrow molecular weight polymers, as shown by size exclusion chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2108–2115, 2002     

Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity

Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N₂ and the resulting reactive species initiate C−H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C−H activation reactions. The sulfonyl nitrene radical anion is the least reactive and its reactivity is governed by the proton coupled electron transfer mechanism. In contrast, sulfonyl nitrene and sulfonyl amidyl radicals react via hydrogen atom transfer pathways. These reactivities and detailed characterization of the radicals with vibrational spectroscopy and with DFT calculations provide information necessary for taking control over the reactivity of these intermediates.     

Electrochemically Driven Swinging of a Nitrobenzyl Pendant Arm in a Nickel Scorpionand Complex

A radical anion −NO₂^.− is formed upon an electrochemically reversible one-electron reduction of the square-planar Ni^II complex of N-nitrobenzylcyclam. The −NO₂^.− group goes to occupy an axial position of the metal ion, thus establishing a significant electronic interaction with the metal center. In particular, the ESR spectrum supports the occurrence of an electron transfer from −NO₂^.− to the metal, which therefore presents a significant Ni^I character. On re-oxidation, the nitrobenzyl side chain detaches and the Ni^II complex is restored, providing an example of a fully reversible redox driven intramolecular motion.     

A New Photochemical Reaction of Sulfonic Acid Esters

Abstract

In 1968 Zen and coworkers reported that thep-tolylsulfonyl group could be removed from carbohydrate systems by photochemical reaction (eq 1).¹ Since then other investigators have used this deprotection process in carbohydrate synthesis.^2-10 Mechanistic studies^11-16 have shown that tosylate photolysis is promoted by compounds (e.g., triethylamine) that donate an electron to an excitedp-toluenesulfonate to generate a radical anion (1). This intermediate then fragments to form the anion of the deprotected sugar (Scheme 1). Since generating a radical anion is the central element in this photochemical process, structural changes that impact radical anion formation should influence the reaction. Replacing the p - tolylsulfonyl group with the pentafluorophenylsulfonyl group generates a more stable radical anion (2) because the electronegative fluorine atoms can help stabilize the negative charge. Since we have a continuing interest in the photochemistry of sulfonic acid esters, we synthesized the pentafluorobenzenesulfonates (pentaflates) 3-6 and studied their photochemistry under electron transfer conditions.     

Tetrathiafulvalene‐Based Mixed‐Valence Acceptor–Donor–Acceptor Triads: A Joint Theoretical and Experimental Approach

This work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)‐based acceptor–donor–acceptor triads (BQ–TTF–BQ and BTCNQ–TTF—BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano‐p‐quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum‐chemical calculations. Emphasis is placed on the mixed‐valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ–TTF–BQ and BTCNQ–TTF–BTCNQ triads in their radical anion states behave as class‐II mixed‐valence compounds with significant electronic communication between the acceptor moieties. Density functional theory calculations (BLYP35/cc‐pVTZ), taking into account the solvent effects, predict charge‐localised species (BQ ^{. ?}–TTF–BQ and BTCNQ ^{. ?}–TTF–BTCNQ) as the most stable structures for the radical anion states of both triads. A stronger localisation is found both experimentally and theoretically for the BTCNQ–TTF–BTCNQ anion, in accordance with the more electron‐withdrawing character of the BTCNQ acceptor. CASSCF/CASPT2 calculations suggest that the low‐energy, broad absorption bands observed experimentally for the BQ–TTF–BQ and BTCNQ–TTF–BTCNQ radical anions are associated with the intervalence charge transfer (IV‐CT) electronic transition and two nearby donor‐to‐acceptor CT excitations. The study highlights the molecular efficiency of the electron‐donor TTF unit as a molecular wire connecting two acceptor redox centres.     

Consecutive Charging of a Perylene Bisimide Dye by Multistep Low-Energy Solar-Light-Induced Electron Transfer Towards H2 Evolution

A photocatalytic system containing a perylene bisimide (PBI) dye as a photosensitizer anchored to titanium dioxide (TiO₂) nanoparticles through carboxyl groups was constructed. Under solar-light irradiation in the presence of sacrificial triethanolamine (TEOA) in neutral and basic conditions (pH 8.5), a reaction cascade is initiated in which the PBI molecule first absorbs green light, giving the formation of a stable radical anion (PBI^.−), which in a second step absorbs near-infrared light, forming a stable PBI dianion (PBI²⁻). Finally, the dianion absorbs red light and injects an electron into the TiO₂ nanoparticle that is coated with platinum co-catalyst for hydrogen evolution. The hydrogen evolution rates (HERs) are as high as 1216 and 1022 μmol h⁻¹ g⁻¹ with simulated sunlight irradiation in neutral and basic conditions, respectively.     

Intermolecular Complexes of Active Oxygen Forms with Amino Acids. A Theoretical Study

Ab initio quantum-chemical calculations were used to examine the thermodynamic aspects of binding of molecular oxygen and the radical anion O₂ ^·- with certain amino acids. It was shown that amino acids form no stable systems with molecular oxygen but form thermodynamically stable complexes with the superoxide radical anion.     

Photocatalysis with Quantum Dots and Visible Light: Selective and Efficient Oxidation of Alcohols to Carbonyl Compounds through a Radical Relay Process in Water

Selective oxidation of alcohols to aldehydes/ketones has been achieved with the help of 3‐mercaptopropionic acid (MPA)‐capped CdSe quantum dot (MPA‐CdSe QD) and visible light. Visible‐light‐prompted electron‐transfer reaction initiates the oxidation. The thiyl radical generated from the thiolate anion adsorbed on a CdSe QD plays a key role by abstracting the hydrogen atom from the C−H bond of the alcohol (R¹CH(OH)R²). The reaction shows high efficiency, good functional group tolerance, and high site‐selectivity in polyhydroxy compounds. The generality and selectivity reported here offer a new opportunity for further applications of QDs in organic transformations.     

Vibrational Spectroscopy of the Dehydrogenated Uracil Radical by Autodetachment of Dipole‐Bound Excited States of Cold Anions

Molecules with large enough dipole moments can bind an electron by the dipole field, which has little effect on the molecular core. A molecular anion can be excited to a dipole‐bound state, which can autodetach by vibronic coupling. Autodetachment spectroscopy of a complex anion cooled in a cryogenic ion trap is reported. Vibrational spectroscopy of the dehydrogenated uracil radical is obtained by a dipole‐bound state with partial rotational resolution. Fundamental frequencies for 21 vibrational modes of the uracil radical are reported. The electron affinity of the uracil radical is measured accurately to be 3.4810±0.0006 eV and the binding energy of the dipole‐bound state is measured to be 146±5 cm^?1. The rotational temperature of the trapped uracil anion is evaluated to be 35 K.     

Indeno[2,1-a]fluorene-11,12-dione Radical Anions: Synthesis,Characterization, and Properties

The one-electron reduction of indeno[2,1-a]fluorene-11,12-dione ( IF ) with various alkali metals prepare the radical anion salts. The data about different structures, properties, and characterization was obtained by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) measurements, and physical property measurement system (PPMS). Compound IF ^.−K⁺(18-c-6) is regarded as a one-dimensional magnetic chain through C−H⋅⋅⋅C interaction. Theoretical calculations and magnetic results showed that [ IF ^.−K⁺(15-c-5)]₂ is a dimer with an open-shell ground state. Compounds IF ^.−Na⁺(15-c-5) and IF ^.−K⁺(cryptand) are monoradical anion salts: IF ₂^.−Li⁺ possesses unique π-stack structure with an interplanar separation less than 3.46 Å, making it a semiconductor (δ_RT=1.9×10⁻⁴ S ⋅ cm⁻¹). This work gives insights into multifunctional radical anions, and describes the design and development of different functional radicals.     

Neutral Boryl Radicals in Mixed-Valent B(III)Br-B(II) Adducts

The general strategies to stabilize a boryl radical involve single electron delocalization by π-system and the steric hinderance from bulky groups. Herein, a new class of boryl radicals is reported, with intramolecular mixed-valent B^(III)Br-B^(II) adducts ligated by a cyclic (alkyl)(amino)carbene (CAAC). The radicals feature a large spin density on the boron center, which is ascertained by EPR spectroscopy and DFT calculations. Structural and computational analyses revealed that the stability of radical species was assisted by the CAAC ligand and a weak but significant B(III)Br-B(II) interaction, suggesting a cooperative avenue for stabilization of boryl radicals. Two-electron reduction of these new boryl radicals provides C−H insertion products via a borylene intermediate.     

Anion⋅⋅⋅Anion Interactions Involving σ-Holes of Perrhenate,Pertechnetate and Permanganate Anions

In this communication experimental and theoretical results are reported affording strong evidence that interactions between electron rich atoms and the metal of tetroxide anions of group 7 elements are a new case of attractive and σ-hole interactions. Single crystal X-ray analyses, molecular electrostatic potentials, quantum theory of atoms-in-molecules, and noncovalent interaction plot analyses show that in crystalline permanganate and perrhenate salts the metal in Mn/ReO₄⁻ anion can act as electron acceptors, the oxygen of another Mn/ReO₄⁻ anion can act as the donor and supramolecular anionic dimers or polymers are formed. The name matere bond (MaB) is proposed to categorize these noncovalent interactions and to differentiate them from the classical metal-ligand coordination bond.     

Hydrogen-Bonded Polyrotaxane Cation Structure in Nickel Dithiolate Anion Radical Salts: Ferromagnetic and Semiconducting Behavior Associated with Structural Phase Transition

The pseudo-polyrotaxane structure of [(H-bpy⁺)- (DB-24-crown-8)]_∞ (H-bpy⁺ = monoprotonated 4,4-bipyridinium; DB-24-crown-8 = dibenzo-24-crown-8) has been incorporated into the anion radical salt [Ni(dmit)₂]⁻ (dmit²⁻ = 1,3-dithiole-2-thione-4,5-dithiolate). (H-bpy⁺)(DB-24-crown-8)[Ni(dmit)₂]⁻ crystallized as two polymorphs, crystals 1 and 2 . Crystal 1 was found to have a lower density and looser packing structure in which H-bpy⁺ forms a one-dimensional hydrogen-bonding chain that passes though the crown ether ring of DB-24-crown-8. DB-24-crown-8 adopts a U-shaped conformation in which two phenylene rings sandwich one of the pyridyl rings of H-bpy⁺ to stabilize the structure. The [Ni(dmit)₂]⁻ anions are arranged in a layer parallel to the (10) plane with uniform side-by-side interactions. A structural phase transition was observed at 235 K, accompanied by ordering of the polyrotaxane structure. In crystal 1 , at 173 K, H-bpy⁺ is twisted around the central C−C bond, which perturbs the arrangement of [Ni(dmit)₂]⁻ through short C−H⋅⋅⋅S contacts. As a result, the semiconducting behavior, with an activation energy of 0.21 eV, becomes insulating below 235 K. The crystal exhibits ferromagnetic interactions because of the weak side-by-side interactions between [Ni(dmit)₂]⁻ anions. Crystal 2 has a similar pseudo-polyrotaxane structure but showed no phase transition. This suggests that the looser crystal packing in crystal 1 induces the structural change of the pseudo-polyrotaxane, perturbing the electron system of [Ni(dmit)₂]⁻.     

On the stability and structure of β-fluoro-substituted radical anions of acetamides. An EPR study at 3 K

An EPR study at 3 K of X-ray irradiated monofluoroacetamide does not reveal a radical anion species, despite the fact that the radical anion in trifluoroacetamide is stable at 77 K. This difference in stability has been found to be dependent on the conformation of the -CF₃ group (eclipsed) versus the -CFH₂ group (staggered). The eclipsed conformation permits effective σ-π hyperconjugation in stabilizing the radical anion. An INDO calculation of CF₃CONH₂^? suggests that the radical site is pyramidal rather than planar with a non-planar angle of 32° and a dihedral angle for the eclipsed fluorine, relative to the nearly π-like orbital, of 30°.     

The Divergent Dimerization Behavior of N‐Substituted Dicyanomethyl Radicals: Dynamically Stabilized versus Stable Radicals

Herein, we demonstrate that the dimerization behavior of amine‐substituted dicyanomethyl radicals can be switched from σ‐ to π‐dimerization simply by varying the electron‐donating substituents. For dicyanomethyl radicals with a 4,4′‐ditolylamine ( DT^. ) or a phenothiazine ( PT^. ) substituent, the monomeric radical form and the corresponding dimer connected by a reversible C−C bond (σ‐dimer) are in equilibrium in solution. On the other hand, the radical with the julolidine skeleton ( JD^. ) does not undergo σ‐dimerization and was isolated as a stable radical in spite of the absence of bulky protecting groups. X‐ray single‐crystal analysis revealed that JD^. forms the π‐dimer in the crystalline state, and variable‐temperature spectroscopy showed that JD^. is in equilibrium with the π‐dimer in toluene solution. DFT calculations point to the importance of electrostatic interactions as a driving force for the π‐dimerization of JD^. because of its polarized structure.     

Radical ions : XXVII. Radical ions of tetrakis(trimethylsilyl)butatriene

One-electron oxidation and one-electron reduction of the electron-rich acetylene derivative, hexakis(trimethylsilyl)-2-butyne [H₃C₃)₃Si]₃CCCC[Si(CH₃)₃]₃, unexpectedly produce the persistent radical cation and radical anion of the hitherto unknown neutral compound, tetrakis(trimethylsilyl)butatriene (R₃Si)₂CCCC(SiR₃)₂. The radical anion can also be generated from the corresponding diacetylene, bis(trimethylsilyl)-1,3-butadiyne R₃SiCCCCSiR₃ and potassium metal, obviously via disproportionation. Photoelectron and electron spin resonance spectroscopic data permit the detection and characterization of the individual species. The stability of both the radical anion and the radical cation of the same molecule can be rationalized by the unique combination of the twofold butatriene π-system with 4 R₃Si substituents, which can act either as electron donors or electron acceptors and thus stabilize the ground state of either the cation or the anion.     

Electron impact studies. CXXIV—Negative ion mass spectra of organic functional groups. Thioacetanilides

The thioacetanilide negative molecular ion (produced by secondary electron capture) is stable, but it fragments after collisional activation to yield [C₆H₅NH]^? by cleavage α to the C?S grouping. The negative molecular ions of (substituted) o-nitrothioacetanilides undergo a series of extremely complex rearrangement reactions. For example, the molecular anion derived from o-nitro-N-methylthioacetanilide yields both acetate and thioacetate anions as major fragment ions.