In this work, the aromatic fluctuation index (FLU) that describes the fluctuation of electronic charge between adjacent atoms in a given ring is introduced as a new aromaticity measure. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized circulation of π electrons. It is defined not only considering the amount of electron sharing between contiguous atoms, which should be substantial in aromatic molecules, but also taking into account the similarity of electron sharing between adjacent atoms. For a series of rings in 15 planar polycyclic aromatic hydrocarbons, we have found that, in general, FLU is strongly correlated with other widely used indicators of local aromaticity, such as the harmonic-oscillator model of aromaticity, the nucleus independent chemical shift, and the para-delocalization index (PDI). In contrast to PDI, the FLU index can be applied to study the aromaticity of rings with any number of members and it can be used to analyze both the local and global aromatic character of rings and molecules.
REFERENCES
1.
2.
3.
4.
T. M.
Krygowski
and M. K.
Cyrański
, Chem. Rev. (Washington, D.C.)
101
, 1385
(2001
).5.
F.
De Proft
and P.
Geerlings
, Chem. Rev. (Washington, D.C.)
101
, 1451
(2001
).6.
A. R.
Katritzky
, K.
Jug
, and D. C.
Oniciu
, Chem. Rev. (Washington, D.C.)
101
, 1421
(2001
).7.
J.
Gomes
and R. B.
Mallion
, Chem. Rev. (Washington, D.C.)
101
, 1349
(2001
);8.
S. W.
Slayden
and J. F.
Liebman
, Chem. Rev. (Washington, D.C.)
101
, 1541
(2001
).9.
T. M.
Krygowski
, M. K.
Cyrański
, Z.
Czarnocki
, G.
Häfelinger
, and A. R.
Katritzky
, Tetrahedron
56
, 1783
(2000
).10.
J.
Kruszewski
and T. M.
Krygowski
, Tetrahedron Lett.
13
, 3839
(1972
).11.
12.
P. V. R.
Schleyer
, C.
Maerker
, A.
Dransfeld
, H.
Jiao
, and N. J. R.
van Eikema Hommes
, J. Am. Chem. Soc.
118
, 6317
(1996
).13.
V. I. Minkin, M. N. Glukhovtsev, and B. Y. Simkin, Aromaticity and Antiaromaticity: Electronic and Structural Aspects (Wiley, New York, 1994).
14.
P.
George
, M.
Trachtman
, C. W.
Bock
, and A. M.
Brett
, J. Chem. Soc., Perkin Trans. 2
1977
, 1036
;M. N.
Glukhovtsev
and P. V. R.
Schleyer
, Chem. Phys. Lett.
198
, 547
(1992
);15.
16.
17.
18.
A.
Savin
, R.
Nesper
, S.
Wengert
, and T. F.
Fassler
, Angew. Chem., Int. Ed. Engl.
36
, 1809
(1997
).19.
20.
J. C.
Santos
, W.
Tiznado
, R.
Contreras
, and P.
Fuentealba
, J. Chem. Phys.
120
, 1670
(2004
);C.
Lepetit
, M. B.
Nielsen
, F.
Diederich
, and R.
Chauvin
, Chem.-Eur. J.
9
, 5056
(2003
).21.
R. F. W.
Bader
and M. E.
Stephens
, J. Am. Chem. Soc.
97
, 7391
(1975
).22.
X.
Fradera
, M. A.
Austen
, and R. F. W.
Bader
, J. Phys. Chem. A
103
, 304
(1999
).23.
J.
Poater
, X.
Fradera
, M.
Duran
, and M.
Solà
, Chem.-Eur. J.
9
, 400
(2003
).24.
R. F. W. Bader, Atoms in Molecules: A Quantum Theory (Clarendon, Oxford, 1990);
25.
J.
Poater
, X.
Fradera
, M.
Duran
, and M.
Solà
, Chem.-Eur. J.
9
, 1113
(2003
).26.
M. K.
Cyrański
, T. M.
Krygowski
, A. R.
Katritzky
, and P. V. R.
Schleyer
, J. Org. Chem.
67
, 1333
(2002
).27.
A. R.
Katritzky
, M.
Karelson
, S.
Sild
, T. M.
Krygowski
, and K.
Jug
, J. Org. Chem.
63
, 5228
(1998
).28.
A.
Savin
, A. D.
Becke
, J.
Flad
, R.
Nesper
, H.
Preuss
, and H. G.
Vonschnering
, Angew. Chem., Int. Ed. Engl.
30
, 409
(1991
);29.
X.
Fradera
, J.
Poater
, S.
Simon
, M.
Duran
, and M.
Solà
, Theor. Chem. Acc.
108
, 214
(2002
).30.
R. F. W. Bader, in Localization and Delocalization in Quantum Chemistry, edited by O. Chalvet, R. Daudel, S. Diner, and J. P. Malrieu (Reidel, Dordrecht, 1975), Vol. I, p. 15;
P. Claverie and S. Diner, ibid., edited by O. Chalvet, R. Daudel, S. Diner, and J. P. Malrieu (Reidel, Dordrecht, 1976), Vol. II, p. 395.
31.
S.
Noury
, A.
Colonna
, and A.
Savin
, J. Mol. Struct.: THEOCHEM
450
, 59
(1998
).32.
W. J.
Hehre
, R.
Ditchfield
, and J. A.
Pople
, J. Chem. Phys.
56
, 2257
(1972
);M.
Francl
, W. J.
Pietro
, W. J.
Hehre
, J. S.
Binkley
, M. S.
Gordon
, D. J.
Frees
, and J. A.
Pople
, J. Chem. Phys.
77
, 3654
(1982
).33.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., A11 GAUSSIAN 98, Revision A11, Pittsburgh, PA, 1998.
34.
W. J. Hehre, L. Radom, P. V. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory (Wiley, New York, 1986).
35.
K.
Wolinski
, J. F.
Hilton
, and P.
Pulay
, J. Am. Chem. Soc.
112
, 821
(1990
).36.
I.
Morao
, B.
Lecea
, and F. P.
Cossio
, J. Org. Chem.
62
, 7033
(1997
);F. P.
Cossio
, I.
Morao
, H. J.
Jiao
, and P. V. R.
Schleyer
, J. Am. Chem. Soc.
121
, 6737
(1999
).37.
P. V. R.
Schleyer
, M.
Manoharan
, Z. X.
Wang
, B.
Kiran
, H. J.
Jiao
, R.
Puchta
, and N. J. R.
van Eikema Hommes
, Org. Lett.
3
, 2465
(2001
).38.
E. Matito, J. Poater, M. Duran, and M. Solà, J. Mol. Struct.: THEOCHEM (submitted).
39.
C.
Corminboeuf
, T.
Heine
, G.
Seifert
, P. V. R.
Schleyer
, and J.
Weber
, Phys. Chem. Chem. Phys.
6
, 273
(2004
).40.
F. W.
Biegler-König
, R. F. W.
Bader
, and T.-H.
Tang
, J. Comput. Chem.
3
, 317
(1982
).41.
42.
43.
P. Lazzeretti, in Progress in Nuclear Magnetic Resonance Spectroscopy, edited by J. W. Emsley, J. Feeney, and L. H. Sutcliffe (Elsevier, Amsterdam, 2000), Vol. 36, p. 1;
44.
M. V.
Zhigalko
, O. V.
Shishkin
, L.
Gorb
, and J.
Leszczynski
, J. Mol. Struct.: THEOCHEM
693
, 153
(2004
).45.
X.
Li
, A. E.
Kuznetsov
, H.-F.
Zhang
, A.
Boldyrev
, and L.-S.
Wang
, Science
291
, 859
(2001
);F.
De Proft
, P. W.
Fowler
, R. W. A.
Havenith
, P. V. R.
Schleyer
, G.
Van Lier
, and P.
Geerlings
, Chem.-Eur. J.
10
, 940
(2004
);M.
Lein
, J.
Frunzke
, and G.
Frenking
, Angew. Chem., Int. Ed.
42
, 1303
(2003
);R. W. A.
Havenith
, P. W.
Fowler
, E.
Steiner
, S.
Shetty
, D.
Kanhere
, and S.
Pal
, Phys. Chem. Chem. Phys.
6
, 285
(2004
).46.
See EPAPS Document No. E-JCPSA6-121-310448 for the NICS at the RCP and the HOMA, NICS, FLU, and PDI calculated at the level of theory for selected systems.
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