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Chemphyschem ; 13(11): 2721-8, 2012 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-22693143


The UV (λ>305 nm) photolysis of triazide 3 in 2-methyl-tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D(T)=0.92 cm(-1), E(T)=0 cm(-1)), quintet dinitrene 6 (g=2.003, D(Q)=0.204 cm(-1), E(Q)=0.035 cm(-1)), and septet trinitrene 8 (g=2.003, D(S)=-0.0904 cm(-1), E(S) =-0.0102 cm(-1)). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ∼1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line-shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line-broadening parameters Γ(E(Q))=180 MHz for dinitrene 6 and Γ(E(S))=330 MHz for trinitrene 8. According to these line-broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6-311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one-center spin-spin interactions in combination with weak positive two-center spin-spin interactions, as predicted by theoretical considerations.

J Phys Chem A ; 115(30): 8419-25, 2011 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-21682299


Photolysis of 2,6-bis(4'-azidophenyl)-4-phenylpyridine in 2-methyltetrahydrofuran (2MTHF) glass at 7 K leads to quintet 2,6-bis(4'-nitrenophenyl)-4-phenylpyridine as a mixture of rotational isomers. The electron spin resonance (ESR) spectrum of this mixture of rotamers shows a considerable broadening of many transitions in the range of 0-5000 G and cannot be reproduced by computer simulations solely based on the tuning of the spin Hamiltonian parameters g, D(Q), and E(Q) alone or on predictions of DFT calculations. The best modeling of the experimental ESR spectrum is obtained only when the large line-broadening parameter of Γ(E(Q)) = 1200 MHz along with the spin Hamiltonian g = 2.003, D(Q) = 0.154 cm(-1), and E(Q) = 0.050 cm(-1) is used in the spectral simulations. The most accurate theoretical estimations of the magnetic parameters of the dinitrene in a 2MTHF glass are obtained from the B3LYP/6-311+G(d,p)+PBE/DZ/COSMO calculations of the spin-spin coupling parameters D(SS) and E(SS). Such calculations overestimate the E(Q) and D(Q) values of the dinitrene just by 1% and 10%, respectively, demonstrating that contributions of the spin-orbit coupling parameters D(SOC) and E(SOC) to the total D(Q) and E(Q) values are negligibly small. The research shows that ESR studies of polynuclear high-spin nitrenes, obtained by photolysis of rotational isomers of the starting azides, can only be successful if large E(Q) strain effects are taken into account in the spectral simulations.

Piridinas/química , Teoria Quântica , Espectroscopia de Ressonância de Spin Eletrônica , Estrutura Molecular , Fotólise , Estereoisomerismo