1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
Authors: Heynderickx, Arnault; Nenon, Sebastien; Siri, Olivier; Lokshin, Vladimir; Khodorkovsky, Vladimir
Abstract
The synthesis and properties of 1,2,3,4-tetrahydro-1,4,5,8-tetraazaanthracene (THTAA) - a heterocycle involving both >N-H donating and =N-accepting moieties - have been reinvestigated. Unlike previously reported, THTAA is a thermally stable compound that can be re-sublimed at 300-310 degrees C without decomposition. Controlled introduction of substituents at the nitrogen atoms of THTAA led to variation of its electron donor/acceptor capability that allowed fine-tuning the absorption properties. The propensity of these compounds and a number of its derivatives to form infinite chains involving >N-H center dot center dot center dot N= and >N-H center dot center dot center dot Hal(-)center dot center dot center dot N+ atoms is demonstrated by X-ray structure analysis. The DFT level optimized and experimental geometry of THTAA and its derivatives show considerable loss of aromaticity within the quinoxaline moiety.
Features of Magnetic Behavior in the Row of Pentacoordinated Bis-o-Iminobenzosemiquinonato Metal (Al, Ga, In) Complexes
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Authors: Ershova, Irina V.; Bogomyakov, Artem S.; Fukin, Georgy K.; Piskunov, Alexandr V.
Abstract
The series of pentacoordinated bis-o-iminobenzosemiquinonato complexes with general formula (imSQ)(2)MR where imSQ - is a radical anion of 4,6-di-tert-butyl-N-(2,6-di-isopropylphenyl)-o-iminobenzoquinone (M = Al, Ga, In; R = Akl, Hal, N-3, NCS) has been expanded through synthesis of six new (imSQ)(2)MR complexes [M = In, R = Me (1), Br (5), Cl (6); M = Ga, R = OPh (16), NCO (17); M = Al, R = NCO (23)]. In all complexes (imSQ)(2)MR except for R = Alk the strong antiferromagnetic exchange coupling between organic radicals, conditioned by the presence of the pathway for superexchange, takes place. In the (imSQ)(2)GaR complexes the value of magnetic exchange interaction (J) was found to depend linearly on the distance between metal center and inorganic apical substituent: the shortening of Ga-R distance in the row Ga-I > Ga-Br > Ga-Cl > Ga-NCS > Ga-OPh is accompanied by the increasing of J value from -68.6 to -139.3 cm(-1). For Al and In analogues complexes such dependence has not been observed. The pathway for superexchange in pentacoordinated (imSQ)(2)MR complexes was found to be broken after complex coordination geometry changeover to hexacoordinated one, which was clearly demonstrated by the example of pyridine molecule coordination to the (imSQ)(2)InI (4).