The aromaticity of verdazyl radicals and their closed-shell charged species
作者： Rashid R. Valiev , Anna K. Drozdova , Pavel V. Petunin , Pavel S. Postnikov , Marina E. Trusova
DOI: 10.1039/C8NJ04341H
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摘要: The aromaticity of fourteen 3-oxo-verdazyl (1–8, 15) and Kuhn verdazyl (9–14) radicals with different substituents has been investigated computationally using the gauge-including magnetically induced current-density (GIMIC) method. strength local global diatropic paratropic ring current obtained by performing numerical integration density flow. Detailed studies densities show that aromatic character obeys Huckel's rule. cations formally 6π electrons in are weakly anions 8π antiaromatic. neutral is found to be studied molecules sustain a significant flows around phenyl rings suggesting there strong coupling between rings. For cations, weaker. spin-current forming 3-oxo-verdazyls, whereas verdazyls we spin mainly localized on nitrogens. calculated ionization potentials also compared values deduced from cyclic voltammetry data.
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sci-hub.se 参考文章(44)
Robin Hicks, Stable radicals : fundamentals and applied aspects of odd-electron compounds Wiley. ,(2010) , 10.1002/9780470666975
Victoria Chemistruck, Dallas Chambers, David J. R. Brook, Structure-Property Relationships of Stable Free Radicals: Verdazyls with Electron-Rich Aryl Substituents Journal of Organic Chemistry. ,vol. 74, pp. 1850- 1857 ,(2009) , 10.1021/JO8019829
Heike Fliegl, Stefan Taubert, Olli Lehtonen, Dage Sundholm, The gauge including magnetically induced current method Physical Chemistry Chemical Physics. ,vol. 13, pp. 20500- 20518 ,(2011) , 10.1039/C1CP21812C
Florian Weigend, Reinhart Ahlrichs, Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Physical Chemistry Chemical Physics. ,vol. 7, pp. 3297- 3305 ,(2005) , 10.1039/B508541A
E. Dormann, W. Dyakonow, B. Gotschy, A. Lang, H. Naarmann, B. Pilawa, N. Walker, H. Winter, Magnetic properties of 1,3,5,6-tetraphenyl- and related verdazyls Synthetic Metals. ,vol. 56, pp. 3273- 3278 ,(1993) , 10.1016/0379-6779(93)90114-C
V. Van Speybroeck, K. Hemelsoet, M. Waroquier, G. B. Marin, Reactivity and aromaticity of polyaromatics in radical cyclization reactions International Journal of Quantum Chemistry. ,vol. 96, pp. 568- 576 ,(2004) , 10.1002/QUA.10758
Chengteh Lee, Weitao Yang, Robert G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Physical Review B. ,vol. 37, pp. 785- 789 ,(1988) , 10.1103/PHYSREVB.37.785
Yasushi Morita, Shinsuke Nishida, Tadahiro Kobayashi, Kozo Fukui, Kazunobu Sato, Daisuke Shiomi, Takeji Takui, Kazuhiro Nakasuji, The first bowl-shaped stable neutral radical with a corannulene system: synthesis and characterization of the electronic structure. Organic Letters. ,vol. 6, pp. 1397- 1400 ,(2004) , 10.1021/OL0497786
Georgina Rayner, Timothy Smith, William Barton, Mark Newton, Robert J. Deeth, Ivan Prokes, Guy J. Clarkson, David M. Haddleton, A comparison of verdazyl radicals modified at the 3-position as mediators in the living radical polymerisation of styrene and n-butyl acrylate Polymer Chemistry. ,vol. 3, pp. 2254- 2260 ,(2012) , 10.1039/C2PY20217D
Emily C. Paré, David J. R. Brook, Aaron Brieger, Mick Badik, Marie Schinke, Synthesis of 1,5-diisopropyl substituted 6-oxoverdazyls Organic and Biomolecular Chemistry. ,vol. 3, pp. 4258- 4261 ,(2005) , 10.1039/B510075E