Cristina Dubceac

C20H4(C4F8)3: A Fluorine-Containing Annulated Corannulene that Is a Better Electron Acceptor Than C60†

At sixes and sevens: The reaction of corannulene with 35 equivalents of 1,4-C4F8I2 is an efficient and a relatively selective process that yields two main products in which six H atoms are substituted with three C4F8 moieties that form six- and seven-membered rings. Low-temperature photoelectron spectroscopy showed the electron affinity of the major isomer (shown) exceeds that of C60 (2.74±0.02 and 2.689±0.008 eV, respectively).

Selective surface decoration of corannulene.

The reaction of corannulene (C(20)H(10)) with 1,2-C(2)H(4)Hal(2) (Hal = Cl or Br) in the presence of AlCl(3) affords stable nonplanar carbocations C(20)H(10)CH(2)CH(2)Hal(+) (Hal = Cl (1) and Br (2)) with an -CH(2)CH(2)Hal moiety attached to the interior carbon atom of the bowl. In the analogous reaction with 1-bromo-2-chloroethane, the selective (up to 98%) abstraction of chloride is observed with the formation of cation 2. The molecular structures of bowl-shaped carbocations 1 and 2 crystallized as salts with AlCl(4)(-) counterions are revealed by single-crystal X-ray diffraction. The reaction of 2 with methanol or ethanol provides further decoration of the nonplanar polyarene upon the nucleophilic addition of alkoxy groups to the exterior carbon atom of the corannulene moiety. The (1)H NMR investigation of the corresponding products, C(20)H(10)(CH(2)CH(2)Br)(OCH(2)R) (R = H (3) and CH(3) (4)), shows the formation of intramolecular H···O and H···Br hydrogen bonds.

Functionalized Corannulene Carbocations: A Structural Overview

A detailed structural overview of a family of bowl-shaped polycyclic aromatic carbocations of the type [C20 H10 R](+) with different R functionalities tethered to the interior surface of corannulene (C20 H10 ) is provided. Changing the identity of the surface-bound groups through alkyl chains spanning from one to four carbon atoms and incorporating a different degree of halogenation has led to the fine tuning of the bowl structures and properties. The deformation of the corannulene core upon functionalization has been revealed based on X-ray crystallographic analysis and compared for the series of cations with R=CH3 , CH2 Cl, CHCl2 , CCl3 , CH2 CH3 , CH2 CH2 Cl, and CH2 CH2 Br. The resulting carbocations have been isolated with several metal-based counterions, varying in size and coordinating abilities ([AlCl4 ](-) , [AlBr4 ](-) , [(SnCl)(GaCl4 )2 ](-) , and [Al(OC(CF3 )3 )4 ](-) ). A variety of aggregation patterns in the solid state has been revealed based on different intermolecular interactions ranging from cation-anion to π-π stacking and to halogen⋅⋅⋅π interactions. For the [C20 H10 CH2 Cl](+) ion crystallized with several different counterions, the conformation of the R group attached to the central five-membered ring of corannulene moiety was found to depend on the solid-state environment defined by the identity of anions. Solution NMR and UV/Vis investigations have been used to complement the X-ray diffraction studies for this series of corannulene-based cations and to demonstrate their different association patterns with the solvent molecules.

Fluorinated copper(I) carboxylates as advanced tunable p-dopants for organic light-emitting diodes.

Volatile copper(I) benzoates with variable degrees of fluorination are used for p-doping of organic hole-transport layers in single-carrier devices, charge-generation layers, and in organic light-emitting diodes. The charge-transport abilities of the doped materials correlate with the degree and position of the fluorination on the aromatic ring of the carboxylate groups.

Corannulene Molecular Rotor with Flexible Perfluorobenzyl Blades: Synthesis, Structure and Properties

Two members of a new class of organic-acceptor perfluorobenzyl corannulenes were prepared by gas-phase and highly-selective solution-phase reactions at elevated temperatures. The peculiar single-crystal X-ray structure of C5-C20H5(CF2C6F5)5 revealed two high-energy conformers with drastically different bowl depths and orientations of perfluorobenzyl blades; the conformers are alternating in columnar packing arrangements and every pair is sandwiched by toluene molecules.

Experimental and DFT Studies of the Electron‐Withdrawing Ability of Perfluoroalkyl (RF) Groups: Electron Affinities of PAH(RF)n Increase Significantly with Increasing RF Chain Length

Two series of aromatic compounds with perfluoroalkyl (RF ) groups of increasing length, 1,3,5,7-naphthalene(RF )4 and 1,3,5,7,9-corannulene(RF )5 , have been prepared and their electronic properties studied by low-temperature photoelectron spectroscopy (PES) (for gas-phase electron affinity measurements). These and many related compounds were also studied by DFT calculations. The data demonstrate unambiguously that the electron-withdrawing ability of RF substituents increases significantly and uniformly from CF3 to C2 F5 to n-C3 F7 to n-C4 F9 .

Polynuclear Copper(I) Clusters Supported by Carboxylate Ligands with Coordinatively Active Ester Group

Two new copper(I) complexes with polynuclear cores bridged by 4-(ethoxycarbonyl)benzoate ligands, [Cu6(O2CC6H4CO2C2H5)4(O2CCF3)2] (1) and [Cu4(O2CC6H4CO2C2H5)4] (2), have been prepared by ligand exchange method in high yield and fully characterized by X-ray diffraction and spectroscopic techniques. The important role of intermolecular interactions between the polynuclear copper(I) clusters imposed through the coordinatively active dangling ester groups of bridging carboxylate ligands on the solid-state packing and photoluminescent behavior of 1 and 2 has been revealed.