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Resonance structures of benzenoid conjugated radicals

Article  in  Physical Chemistry Chemical Physics · January 1999

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Resonance structures of benzenoid conjugated radicals

Jerry Ray Dias

Department of Chemistry, University of Missouri, Kansas City, MO 64110-2499, USA

Received 2nd August 1999, Accepted 28th September 1999

For comparable size, the number of resonance structures (SC) in radical (non-Kekulean) benzenoid
hydrocarbons is signiÐcantly larger than the number of resonance structures (K) in Kekulean (closed-shell)
benzenoid hydrocarbons. For a given benzenoid size, as the radical multiplicity increases so does SC
(resonance structure count). Analytical expressions for the SC of families of benzenoid radicals have been
derived. Recent experimental evidence for the existence in Ñames of the Ðrst and second generation members to
our constant-isomer benzenoid series is noted. The interconnection of deviations to HundÏs rule, essentially
disconnected pp-electronic systems, and concealed non-Kekulean benzenoids is discussed and illustrated.

Introduction naphthalene to generate relatively large concentrations of high

mass polyaromatic hydrocarbons (PAHs) in so-called Ñat
It is well known that the more resonance structures that can Ñames that have a spatially well resolved reaction zone in
be drawn for a molecule the more stable it is, other things which PAH chemistry takes place. To this reaction zone, they
being equal. Numerous papers and books have been written apply molecular beam mass spectrometry with laser photo-
on analytical expressions and methods for computing the ionization that ionizes PAHs with very little fragmentation.
number of Kekule resonance structures (K) for various classes The mass spectra are deconvoluted with respect to 13C to get
of closed-shell benzenoid hydrocarbons.1,2 The most general intensities of PAHs with the same N (number of formula
C
procedure of Ðnding the number of Kekule structures is the carbons) but di†erent N (number of formula hydrogens).
H
JohnÈSachs determinant method which requires knowledge of These results are supplemented by gas chromatography/mass
the K values for some select smaller benzenoid hydrocar- spectrometry (GC/MS) analysis of the Ñame constituents and
bons.3 This small list of known K values can be further aug- by radical scavenging experiments.
mented with additional ones by a fragmentation method due The experimental results of Homann and coworkers6,12
to Randic who recognized that a bond in a conjugated system conform to our prior published systematics of PAHs.7,13
will be either single or double, leading to the relation of Their mass spectral plots of ion intensities vs. N at N \
C H
K(G) \ K(G [ e) ] K(G [ (e)) where G [ e is a subgraph of constant give curves with maxima occurring at C H
16 10
molecular graph G in which an edge (corresponding to a (pyrene), C H (coronene), C H (structures given on page
24 12 30 14
single bond) has been deleted and G [ (e) is a subgraph in 66 of our Part A book13), C H (ovalene \
32 14
which an edge and its vertices (corresponding to a double circumnaphthalene), C H (page 68, Part A13), C H
40 16 42 16
bond) are deleted together.4 This relation is valid for both (circumpyrene, page 69, Part A13), C H (pages 73È74, Part
50 18
alternant hydrocabons (AHs) and nonalternant hydrocarbons A13) and C H (circumcoronene), and at C H
54 18 13 9
where fragment diradical systems (K \ 0) can be generated in (phenalenyl), C H (benzo[cd]pyrenyl), C H
19 11 27 13
the latter. A molecular graph is a vertexÈline depiction corre- (benzo[bc]coronene), C H (circumphenalenyl), C H
37 15 47 17
sponding to a CÈC r-bond skeleton belonging to a benzenoid (circumbenzo[cd]pyrenyl) and C H (circum-
59 19
which avoids representing it by only one of its many reso- benzo[bc]coronene).7,13,14 Thus, Homann and coworkers
nance structures. have accumulated evidence for the presence of the Ðrst two
In comparison, very little work has been done on the generation members of my constant-isomer series.7,14 Namely,
number of resonance structures (referred to as structure the Ðrst two generations of the D one-isomer series
6h
count \ SC) of benzenoid hydrocarbon radicals (K \ 0).5 (coronene, circumcoronene, . . .) and the matching pair of D
2h
Benzenoid free radicals are major intermediate species in the one-isomer series (naphthalene, ovalene, . . . and pyrene, cir-
formation of fullerenes, soot and related aromatics.6 Our prior cumpyrene, . . .) for the even-carbon benzenoids and the D
3h
work on benzenoid free radicals began with the formulation of one-isomer series (phenalenyl, circumphenalenyl, . . .) and the
a ““ formula periodic table for odd-carbon benzenoid matching pair of C one-isomer series (benzo[cd]pyrenyl,
2v
hydrocarbons ÏÏ [referred to as table PAH6(odd)].7 While all circumbenzo[cd]pyrenyl, ... and benzo[bc]coronene,
odd-carbon benzenoids are always (odd) p-radical species, circumbenzo[bc]coronene, . . .) for the odd-carbon mono-
even-carbon benzenoids are either Kekulean in which all pp- radical benzenoids have been observed in acetylene Ñames.7,14
electrons can be paired or non-Kekulean even p-radical Fig. 1 gives the Ðrst generation members of the monoradical
species. Topological inspection methods for recognizing and diradical constant-isomer series. Note that each (upper)
radical multiplicity for odd- and even-carbon benzenoids and monoradical in Fig. 1 is topologically equivalent in symmetry,
recognizing when the latter were radicals rather than Keku- number of selective lineations (^1 eigenvalues), etc. to the
lean was essential for progress of this work.8h10 Other recent diradical immediately below it per our topological para-
results by the author on radical systems are available.11 digm.14 All these open-shell benzenoids are maximally con-
Homann and coworkers have recently developed an experi- densed and are devoid of bay regions. Fig. 2 more fully
mental setup for the study of fuel-rich hydrocarbon Ñames.6,12 illustrates the monoradical constant-isomer series by showing
Their apparatus uses premixed aromatic fuels like benzene or the second generation members with the excised internal

Phys. Chem. Chem. Phys., 1999, 1, 5081È5086 5081

This journal is ( The Owner Societies 1999

Fig. 1 Benzenoid hydrocarbon radicals that are base members of the
one-isomer series. Note the topological correspondence between the
monoradicals and the diradicals.
structure shown in bold, the latter corresponding to the Ðrst
generation members given in Fig. 1.
In the Ñame, the relative concentration of odd-carbon
PAHs increases strongly with N , and for very large odd-
C (downward pointing vertices on the lower periphery) denoted
carbon PAHs, the radical concentrations exceed those of
closed-shell (Kekulean) even-carbon benzenoids.6 A funda-
mental precept in resonance theory is that the more valence
bond structures that can be drawn for a molecule, the more
resonance it has, which implies greater stability, other things
being equal. Here it will become evident that the number of
resonance structures in p-radical benzenoids escalates much
faster than in Kekulean benzenoids, which suggests that the
energy di†erence between these two classes may approach
zero as their size increases, especially for systems with lower
spin multiplicities.
Because of the importance of p-radical PAHs in the forma-
tion of larger PAHs, fullerenes, and soot, this study was initi-
ated. Furthermore, a number of odd-carbon benzenoid
carbanions and carbocations have been synthesized, and the
information on SC of benzenoid free radicals is directly trans-
ferable to these systems.
Experimental
Since the numerical value of the tail coefficient in the match-
ing polynomial for a conjugated molecular system gives the
number of resonance structures, the matching polynomial
Pascal program of Ramaraj and Balasubramanian15 was used
Fig. 2 The Ðrst (bold insert) and second generation members of the one-isomer series observed in Ñames. C H ] C
recursion relationship for the successive formulas for constant-isomer series. The SC above is for the larger formula.
5082 Phys. Chem. Chem. Phys., 1999, 1, 5081È5086
for many of the results presented herein. However, this
program had certain limitations in accuracy for large systems
requiring the following quality controls. The results were
deemed satisfactory only if the a , a and a coefficients
2 4 6
agreed with those calculated by our equations,16 the coeffi-
cients uniformly increased and then decreased in magnitude
and were all integers, and the tail coefficient index was consis-
tent with the radical multiplicity. If these criteria were not met
in the computer determination of the matching polynomial of
a given radical, it was decomposed into smaller fragments
using a strategy analogous to the method of Randic. The
matching polynomials of these fragments were then deter-
mined. Our decomposition method distinguishes between
starred and unstarred carbon sites on an AH radical system. A
pp-conjugated radical system is maximally starred such that
no two starred sites are adjacent and no two unstarred sites
are adjacent and the larger of the two sets bare stars. If one
examines all the resonance structures of such a starred radical,
it will be observed that the unpaired electrons are only found
on starred sites.
Results and discussion
Recognition of hydrocarbon radicals
A benzenoid structure can be oriented three di†erent ways
with some of its edges (approx. 1/3) in a vertical direction. A
benzenoid structure so oriented has peaks (upward pointing
vertices on the upper periphery) denoted by – and valleys
by —. Gordon and Davison9 have shown that whenever – D
—, then the corresponding benzenoid structure is a radical.
– D — for odd-carbon benzenoid structures. For well
behaved benzenoid systems, – [ — \ 1 for monoradicals,
– [ — \ 2 for diradicals, etc. (cf. Fig. 1). When – \ — the
benzenoid structure may or may not be a radical. If it is a
radical, it is called a concealed (hidden) non-Kekulean benze-
noid (K \ 0)10 or a type 2 radical.8 Many of these type of
radicals have a narrow isthmus of fewer vertical edges than
peaks or valleys.8
Some recent literature examples
Consider the benzenoid hydrocarbons in Fig. 3. Cation salts
of both benzo[cd]perylenyl (C H ) and trinaphtho-
23 13
phenalenyl (C H ) have been isolated and character-
31 15
ized.17,18 Both these cations are ionized homologues of
phenalenyl monoradical. The SC of benzotriangulene was
computed previously by Hosoya and coworkers.19 The
C H molecular graph pair shown in Fig. 3 are the only
33 17
known isospectral benzenoids.20 Isospectral molecular graphs
have exactly the same eigenvalues. Although at the HuŽckel
molecular orbital (HMO) level, these molecular graphs have
identical characteristic polynomials, their matching poly-
H is the general
n s n`2s`6 s`6

Fig. 3 Representative benzenoid hydocarbons from the recent liter-
ature.
nomials are not identical. Still these matching polynomials do
have the same Ðrst few initial and ending coefficients and con-
sequently have the same SC. Thus, while isospectral molecules
do have the same HMO total pp-electronic energy, they do
not always have the same topological resonance energies
(TRE).21
Fig. 4 Fragmentation of a benzenoid by operating on its upper
central starred position per SC(G) \ SC(G [ v ) ] &SC(G [ (e)).
x
this fragmentation equation, consider the two molecular
graphs given in Fig. 5. Selecting the unstarred central peak
vertex exploits their two-fold symmetry. There are only two
edges converging on each of these sites and deletion of either
edge gives the same successor subgraph shown to the right.
Thus, the successor subgraph of triangulene diradical will
have an SC half as large as the SC for triangulene.
Two types of hydrocarbon radicals
Considerable experimental and theoretical work has been
done on the trimethylenemethane (SC \ 3) and bisallyl diradi-
cals (SC \ 4).22h24 Trimethylenemethane diradical has spa-
tially overlapping non-bonding molecular orbitals (NBMOs)

Fragmentation of large hydrocarbon radicals to smaller ones

The following fragmentation relations can be used to decom-
pose a molecular graph of any benzenoid radical into smaller
ones. For the set of all resonance structures of a radical
system, a given starred site will either contain an unpaired
electron or belong to a double bond joining each adjacent
unstarred carbon. This leads to the relation SC(G) \ SC(G
[ v ) ] &SC(G [ (e)) where G [ v is the subgraph resulting
x x
from the deletion of the starred carbon site in graph G. To
illustrate this fragmentation process, consider the C H
40 14
(dibenzo[cd,hi]coronene) diradical molecular graph (G) in Fig.
4. We exploit its two-fold symmetry by selecting the central
uppermost starred site. Its deletion gives the subgraph (G
[ v ) in the upper right-hand location. Vinyl groups attached
x
to unstarred sites make no contribution to SC and can be
pruned o†. Pruning o† the two vinyl groups would give the
molecular graph of anthranaphthacene, which has SC \ 110,
and therefore this subgraph has SC \ 110. Because of the
two-fold symmetry, deletion of the left or right slanting edges
from G(C H ) gives the same subgraph shown in the right-
40 14
hand center of Fig. 4 which corresponds to a diradical of
SC \ 378. Deletion of the vertical edge from G(C H ) gives
40 14
the lower subgraph which after pruning o† the two vinyl
groups gives a molecular graph corresponding to dibenzo[mn,
qr]tetracene having SC \ 390.
Similarly, a given unstarred site will only belong to a
double bond emanating from each attached starred carbon Fig. 5 Fragmentations of benzenoids involving their upper central
leading to the relation of SC(G) \ &SC(G [ (e)). To illustrate unstarred positions per SC(G) \ &SC(G [ (e)).

Phys. Chem. Chem. Phys., 1999, 1, 5081È5086 5083

 Fig. 6 A series of concealed non-Kekulean benzenoid hydrocarbons that are all diradicals.
which are said to be nondisjoint MOs whereas bisallyl has
disjoint NBMOs because they do not overlap. If two electrons
occupy overlapping NBMOs, their motions are correlated if
they have the same spin (triplet state) to prevent them from
being simultaneously in the same region of space thereby
reducing electronÈelectron repulsion. On the other hand if
these two electrons have opposite spins (singlet state), their
motions are not correlated, resulting in closer proximity and
Fig. 7 The benzopolyperinaphthalene monoradical series.
Fig. 8 The benzoacene monoradical series.
5084 Phys. Chem. Chem. Phys., 1999, 1, 5081È5086
greater electronÈelectron repulsion. Thus, under these circum-
stances, the latter singlet state would be destabilized relative
to the triplet state. The exchange integral is more signiÐcant
for correlated electrons, causing the electrons to preferentially
have the same spin in nondisjoint NBMOs. Tri-
methylenemethane diradical has a triplet ground state, and
bisallyl (tetramethyleneethane) diradical having two NBMOs
localized on di†erent sets of carbon atoms has a small
exchange integral resulting in nearly degenerate singlet and
triplet states.23 Bisallyl can be constructed by joining the
central unstarred positions of two allyl radicals. In this way
the NBMO of each allyl unit remains independent of the
other, i.e., they are essentially disconnected. As pointed out by
HuŽckel, the unstarred positions of allyl have zero coefficients
in their NBMOs, resulting in the exchange energy between the
two halves of bisallyl being close to zero.24 Thus, atomic con-
nectivity is a strong determinant of spin multiplicity in non-
Kekulean molecules and provides a basis for predicting
departures from HundÏs rule in organic molecules.
The electronic understanding summarized above that has
been derived by the study of the simpler trimethylenemethane
and bisallyl diradicals can now be extended to the more
complex benzenoid radicals. Triangulene diradical is the ben-
zenoid analog of trimethylenemethane diradical in that both
have triplet ground states, which is consistent with HundÏs
rule. The diradical trianion of trioxytriangulene has been
experimentally shown to exist in a triplet ground state, and
calculations on triangulene itself showed that the triplet state
was 20 kcal mol~1 lower in energy than the singlet.25 Tri-
angulene diradical is an example of an obvious non-Kekulean
benzenoid because K \ 0, it has two more starred carbon ver-
tices than unstarred ones, and the di†erence in the number of
peaks and valleys is two (– [ — \ 2). Biphenalenyl diradical
is a bridged benzenoid analog of bisallyl diradical in that both
have essentially disconnected electronic systems and nearly
degenerate singlet and triplet states.26 Biphenalenyl can be
regarded as the initial member of the series of hourglass-
shaped concealed non-Kekulean benzenoids shown in Fig. 6.
Concealed non-Kekulean benzenoids have the same number
of starred and unstarred carbon vertices leading to the same
number of peaks and valleys (– [ — \ 0). Thus, it appears
that concealed non-Kekulean benzenoids (Fig. 6) may well
exist in the singlet state or have nearly degenerate singlet/
triplet ground states (gs), and, for all general purposes, might
be regarded as being nearly ““ closed-shell systems ÏÏ even
though no Kekule structure can be drawn for them. Typically
Kekulean benzenoids are closed-shell, well behaved even-
carbon radical benzenoid systems (– D —) having odd-
multiplet ground states consistent with HundÏs rule, and
concealed radical (even-carbon) benzenoids have nearly
degenerate singlet/triplet (or odd-multiplet) ground states. As
it will be discussed in the next section, concealed non-

Fig. 9 The naphthoacene monoradical series.
Fig. 10 General molecular graphs corresponding to two series of
diradical benzenoid hydrocarbons.
Fig. 11 Molecular graphs corresponding to the zero generation
member of the series in Figs. 7È10, respectively.
Fig. 12 Construction of a concealed non-Kekulean benzenoid by
joining the unstarred positions of two identical benzo[cd]pyrenes.
Fig. 13 Essentially disconnected Kekulean benzenoid hydrocarbons.
Kekulean benzenoids are the free-radical analogs of essentially
disconnected Kekulean benzenoids.
Series of hydrocarbon radicals and analytical expressions for
SC
Fig. 7 presents a homologous series of strictly peri-condensed
monoradical benzenoids successively built up two rings at a
time by the C H aufbau unit. The Ðrst and second molecular
6 2
graphs of this series correspond to phenalenyl (C H ) and
13 9
benzo[cd]pyrene (C H ) and are the Ðrst generation
19 11
members of the D and C one-isomer series, respectively,
3h 2v
shown in Fig. 1. Also Fig. 7 presents the analytical expression
for the SC vs. a membership index number. This analytical
expression is of degree 4 in n as each successive molecular
graph is incremented by two rings.
Figs. 8 and 9 give two series of monoradicals and analytical
expressions for their SC vs. the number of anellated rings. Fig.
10 presents the general molecular graphs and corresponding
SC equations for two benzenoid diradical series. Each suc-
cessive member of these series is increased by one ring using
the C H (1,3-butadienetetrayl) aufbau unit. The analytical
4 2
expressions for their SC are quadratic in n because each suc-
cessive molecular graph is incremented by one ring.
The zero generation members of the benzenoid series given
in Figs. 7È10 are collected in Fig. 11. Zero generation
members are not strictly benzenoid because they possess side
chains (alkenyl branches). The molecular graph of benzyl is
the zero generation member to the benzopolyperinaphthalene
series in Fig. 7. Setting n \ 0 in the analytical equation for this
series gives SC \ 5 in agreement with that given for benzyl
using the zero-sum rule as described by Herndon.5 According
to this prescription, the sum of the NBMO coefficients of the
starred positions attached to each unstarred position must
equal zero as shown in Fig. 11. The sum of the absolute values
of all the unnormalized integers thus obtained by application
of the zero-sum rule is equal to the SC for the corresponding
molecule. The SC for the molecular graph of 1-phenylallyl, the
zero generation member of the benzoacenes series in Fig. 8,
can similarly be derived.
1-Vinylphenalenyl (C H ) and 11-methylenebenzo[mn]
15 11
anthracene (C H ) and the C H structure in Fig. 11 are
18 12 26 14
the zero generation members of the naphthoacene series (Fig.
9) and the series given in Fig. 10, respectively. The corre-
sponding SC values for these zero generation members are
easily obtained by setting n \ 0 in the respective analytical
expressions given.
The hourglass-shaped benzenoid series in Fig. 6 are all con-
cealed diradicals with an analytical expression for SC which is
the square of the one given in Fig. 7. These molecular graphs
(Fig. 6) can be constructed by joining the unstarred sites of
two identical components from the benzopolyperinaphtha-
lenes series (Fig. 7). To illustrate this construction process,
consider Fig. 12. Benzo[cd]pyrene has been maximally starred
on the right. When two of these systems are joined through
their unstarred sites, we obtain the hourglass-shaped benze-
noid given on the left where the dashed line going through the
Phys. Chem. Chem. Phys., 1999, 1, 5081È5086 5085

Fig. 14 A concealed non-Kekulean benzenoid hydrocarbon analo-
gous to zethrene having a 1,3-butadiene spacer group.
isthmus identiÐes the region of join ; note that the original
starring pattern of each component is shown only for empha-
sis. As in bisallyl, both unpaired electrons are incapable of
moving from one component to the other, and each of their
motions are conÐned to the respective original component. In
e†ect, each component is ““ essentially disconnected ÏÏ, and these
hourglass-shaped benzenoids have SCs that are simply the
products of the SCs of the associated components. Thus, these
concealed non-Kekulean benzenoids are essentially discon-
nected just as perylene, bisanthrene, and zethrene in Fig. 13,
for example, are essentially disconnected.27 Perylene is com-
posed of two essentially disconnected naphthalene com-
ponents, and bisanthrene is composed of two essentially
disconnected anthracene components. Zethrene is made up of
two naphthalene components joined through a 1,3-butadiene
spacer group. A concealed non-Kekulean benzenoid having a
1,3-butadiene spacer group analogous to that of zethrene is
given in Fig. 14. The number of Kekule structures for essen-
tially disconnected Kekulean benzenoids is the product of the
numbers of Kekule structures of the component parts. Other
series and their SC analytical expressions can easily be
obtained by using components from Figs. 9 and 10.
Conclusion
In general, signiÐcantly more resonance structures exist for
free radical benzenoid hydrocarbons than for Kekulean benze-
noid hydrocarbons. Since this di†erence increases with size, it
is suggested that the energy di†erence between these two
classes of benzenoids decreases. This same suggestion has been
put forth by Klein and Bytautas.28 A new method for decom-
posing larger radical benzenoids into smaller ones for the
purpose of determining SC has been developed and illus-
trated. Coupling this with the SC analytical expressions for
the benzenoid radical series contained herein, one should be
able to derive additional analytical expressions for other selec-
ted radical benzenoid series in a fashion similar to what has
been done for the number of Kekule structures.1,2
The special properties of concealed non-Kekulean benze-
noid hydrocarbons have been further revealed in this study.
Typically a concealed non-Kekulean benzenoid hydrocarbon
has an isthmus, is essentially disconnected, has the same
5086 Phys. Chem. Chem. Phys., 1999, 1, 5081È5086
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number of starred and unstarred carbon sites, and equal
numbers of peaks and valleys, and has a nearly degenerate
singlet/triplet ground state.
Acknowledgements
The author is grateful to Professor K. Balasubramanian for
providing him with a diskette of his Pascal Matching Poly-
nomial Program.15
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Paper 9/06250E