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Fullerene “Superhalogen” Radicals: the Substituent Effect on Electronic Properties of 1,7,11,24,27‐C 60 X 5
Author(s) -
Clikeman Tyler T.,
Deng S. H. M.,
Avdoshenko Stanislav,
Wang XueBin,
Popov Alexey A.,
Strauss Steven H.,
Boltalina Olga V.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301234
Subject(s) - radical , chemistry , supramolecular chemistry , fullerene , substituent , x ray photoelectron spectroscopy , electron affinity (data page) , crystallography , halogen , fullerene chemistry , electron paramagnetic resonance , stereochemistry , molecule , crystal structure , organic chemistry , alkyl , physics , nuclear magnetic resonance
Hexasubstituted fullerenes with the skew pentagonal pyramid (SPP) addition pattern are predominantly formed in many types of reactions and represent important and versatile building blocks for supramolecular chemistry, biomedical and optoelectronic applications. Regioselective synthesis and characterization of the new SPP derivative, C 60 (CF 3 ) 4 (CN)H, in this work led to the experimental identification of the new family of “superhalogen fullerene radicals”, species with the gas‐phase electron affinity higher than that of the most electronegative halogens, F and Cl. Low‐temperature photoelectron spectroscopy and DFT studies of different C 60 X 5 radicals reveal a profound effect of X groups on their electron affinities (EA), which vary from 2.76 eV (X=CH 3 ) to 4.47 eV (X=CN). The measured gas‐phase EA of the newly synthesized C 60 (CF 3 ) 4 CN equals 4.28 (1) eV, which is about 1 eV higher than the EA of Cl atom. An observed remarkable stability of C 60 (CF 3 ) 4 CN − in solution under ambient conditions opens new venues for design of air‐stable molecular complexes and salts for supramolecular structures of electroactive functional materials.