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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.
structure shown in bold, the latter corresponding to the Ðrst A benzenoid structure can be oriented three di†erent ways
generation members given in Fig. 1. with some of its edges (approx. 1/3) in a vertical direction. A
In the Ñame, the relative concentration of odd-carbon benzenoid structure so oriented has peaks (upward pointing
PAHs increases strongly with N , and for very large odd- vertices on the upper periphery) denoted by – and valleys
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- by —. Gordon and Davison9 have shown that whenever – D
mental precept in resonance theory is that the more valence —, then the corresponding benzenoid structure is a radical.
bond structures that can be drawn for a molecule, the more – D — for odd-carbon benzenoid structures. For well
resonance it has, which implies greater stability, other things behaved benzenoid systems, – [ — \ 1 for monoradicals,
being equal. Here it will become evident that the number of – [ — \ 2 for diradicals, etc. (cf. Fig. 1). When – \ — the
resonance structures in p-radical benzenoids escalates much benzenoid structure may or may not be a radical. If it is a
faster than in Kekulean benzenoids, which suggests that the radical, it is called a concealed (hidden) non-Kekulean benze-
energy di†erence between these two classes may approach noid (K \ 0)10 or a type 2 radical.8 Many of these type of
zero as their size increases, especially for systems with lower radicals have a narrow isthmus of fewer vertical edges than
spin multiplicities. peaks or valleys.8
Because of the importance of p-radical PAHs in the forma-
Some recent literature examples
tion of larger PAHs, fullerenes, and soot, this study was initi-
ated. Furthermore, a number of odd-carbon benzenoid Consider the benzenoid hydrocarbons in Fig. 3. Cation salts
carbanions and carbocations have been synthesized, and the of both benzo[cd]perylenyl (C H ) and trinaphtho-
23 13
information on SC of benzenoid free radicals is directly trans- phenalenyl (C H ) have been isolated and character-
31 15
ferable to these systems. ized.17,18 Both these cations are ionized homologues of
phenalenyl monoradical. The SC of benzotriangulene was
Experimental computed previously by Hosoya and coworkers.19 The
C H molecular graph pair shown in Fig. 3 are the only
33 17
Since the numerical value of the tail coefficient in the match- known isospectral benzenoids.20 Isospectral molecular graphs
ing polynomial for a conjugated molecular system gives the have exactly the same eigenvalues. Although at the Huckel
number of resonance structures, the matching polynomial molecular orbital (HMO) level, these molecular graphs have
Pascal program of Ramaraj and Balasubramanian15 was used identical characteristic polynomials, their matching poly-
Fig. 2 The Ðrst (bold insert) and second generation members of the one-isomer series observed in Ñames. C H ] C H is the general
n s n`2s`6 s`6
recursion relationship for the successive formulas for constant-isomer series. The SC above is for the larger formula.
which are said to be nondisjoint MOs whereas bisallyl has greater electronÈelectron repulsion. Thus, under these circum-
disjoint NBMOs because they do not overlap. If two electrons stances, the latter singlet state would be destabilized relative
occupy overlapping NBMOs, their motions are correlated if to the triplet state. The exchange integral is more signiÐcant
they have the same spin (triplet state) to prevent them from for correlated electrons, causing the electrons to preferentially
being simultaneously in the same region of space thereby have the same spin in nondisjoint NBMOs. Tri-
reducing electronÈelectron repulsion. On the other hand if methylenemethane diradical has a triplet ground state, and
these two electrons have opposite spins (singlet state), their bisallyl (tetramethyleneethane) diradical having two NBMOs
motions are not correlated, resulting in closer proximity and 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
Huckel, 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-
Fig. 7 The benzopolyperinaphthalene monoradical series. 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
Fig. 8 The benzoacene monoradical series. it will be discussed in the next section, concealed non-
Acknowledgements
The author is grateful to Professor K. Balasubramanian for
providing him with a diskette of his Pascal Matching Poly-
nomial Program.15