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Journal of Molecular Structure: THEOCHEM 863 (2008) 5054

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Journal of Molecular Structure: THEOCHEM


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The isomers of phenalene and their singlet and triplet states: A HartreeFock
and density functional computational investigation
Joan M. Zoellner, Robert W. Zoellner *
Department of Chemistry, Humboldt State University, One Harpst Street, Arcata, CA 95521-8299, USA

a r t i c l e i n f o a b s t r a c t

Article history: Each of the isomers of phenalene, 1H-, 2H-, 3aH-, and 9bH-phenalene, as well as the cation, neutral rad-
Received 29 April 2008 ical, and anion in the phenalenyl system, have been examined at the HartreeFock 6-31G(d) and the den-
Received in revised form 14 May 2008 sity functional B3LYP/6-31G(d) levels of theory. The structures and properties of the phenalenes were
Accepted 16 May 2008
determined as both singlets and triplets. While the data indicate that both the 9bH- and the 1H-isomer
Available online 24 May 2008
will exist as ground state singlets, the 2H- and 3aH-phenalenes are predicted to exist as ground state trip-
lets; only the synthesis of the 1H-isomer has been reported in the literature. Structurally, 1H- and 2H-
Keywords:
phenalene are planar systems, 3aH- and 9bH-phenalene are non-planar systems puckered at the satu-
Phenalene
Phenalenyl
rated carbon, and the cation, neutral radical, and anion of phenalenyl are planar D3h systems.
HartreeFock 2008 Elsevier B.V. All rights reserved.
Density functional
Isomer

1. Introduction tron system [11] through the formal loss of hydride, a neutral 13 p-
electron radical [12,13] from the loss of a neutral hydrogen atom,
The non-benzenoid hydrocarbon 1H-phenalene (1), C13H10, has or a red, anionic 14 p-electron system [8,13] resulting from the loss
been known since the molecule (then termed perinaphthindene) of a proton.
was rst synthesized in low yield by Lock and Gergely [1]. Deriva- The phenalenyl moiety has been incorporated into organome-
tives were reported even earlier [2,3], and Boekelheide and Larra- tallic molecules as a p-donor ligand. In these systems, the ligand
bee later reported improved syntheses of (1), termed may bind to a metal in an g1-mode [14], in an g3-allylic fashion
perinaphthene by these authors [4]. Given the structure of (1), [1416], or in an g6-mode [14,17,18]. Computationally, a lithium,
other isomers, (2), (3), and (4), may be envisioned, as depicted in calcium, or aluminium atom has been shown to form strong cova-
Fig. 1. However, only the 1H-isomer has apparently been investi- lent bonds to the phenalenyl moiety [19]. In addition, 1H-phena-
gated; neither the 2H- nor the 3aH-isomer has been reported, lene itself and derivatives of (1) have been shown to form
while a search of the literature reveals references [57] to the organometallic complexes with a variety of metals [17,18].
9bH-isomer but with no denitive experimental or computational While a signicant amount of information is available for 1H-
data reported. (Careful examination of these references indicates phenalene and for the phenalenyl cation, neutral radical, and an-
that the molecules reported as the 9bH-isomer may actually be re- ion, there is a dearth of information concerning the remaining
ports of the 1H-isomer mistakenly depicted as the 9bH-isomer.) three isomers of phenalene. Herein are reported the results of Har-
The presence of the saturated carbon in each of the phenalene treeFock and density functional computational investigations of
isomers prevents the molecules from exhibiting completely delo- the structures and properties of the phenalene isomers and, for
calized p-systems. In addition, isomers (2) and (3) can be reason- comparison, the phenalene cation, radical, and anion system.
ably expected to exist as ground state triplet diradicaloid
systems because of the impossibility of constructing alternating 2. Theoretical approach
single and double bonds to all of the unsaturated carbon atoms
in these molecules. However, in all of these isomers, the loss of All HartreeFock calculations were carried out using both the PC
the hydrogen moiety results in the formation of a phenalenyl sys- Spartan Pro computational package [20] and Gaussian 98W [21];
tem [810], C13H9. The phenalenyl system (5) itself is somewhat density functional calculations were carried out using Gaussian
unique in that phenalenyl, C13H9, can exist as a cationic 12 p-elec- 98W. To assure the existence of stable minima, vibrational frequen-
cies for each molecule were determined at both the HartreeFock
* Corresponding author. Tel.:+ 1 707 826 3244; fax:+ 1 707 826 3279.
and density functional levels of theory. The methods used for sin-
E-mail address: rwz7001@humboldt.edu (R.W. Zoellner). glet systems were RHF/6-31G(d) [22] and B3LYP/6-31G(d) [23];

0166-1280/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2008.05.017
J.M. Zoellner, R.W. Zoellner / Journal of Molecular Structure: THEOCHEM 863 (2008) 5054 51

H H
H
H

1H-phenalene (1) 2H-phenalene (2)

H
Fig. 2. The singlet structures of 1H-phenalene (1), left, and 9bH-phenalene (4),
3aH-phenalene (3) 9bH-phenalene (4) right. While the carbon atoms of (1) lie nearly exactly in a plane, (4) is denitely
puckered at C9b.

+,0,-

phenalenyl (5)

Fig. 1. The four possible phenalene isomers and the phenalenyl system. Note that
neither (2) nor (3) can be represented in a standard valence bond depiction except
as a set of diradicaloid resonance structures.

the corresponding UHF/6-31G(d) and UB3LYP/6-31G(d) methods


were employed for the triplet systems. No symmetry constraints
were used in any of the calculations. Fig. 3. The triplet structures of 2H-phenalene (2), left, and 3aH-phenalene (3), right.
While the carbon atoms of (2) are nearly exactly planar, (3) is denitely puckered at
3. Results and discussion C3a.

Selected calculated properties for the phenalene isomers as


both singlet and triplet molecules, as well as for the cation, neutral For 2H-phenalene (2), the triplet is more stable than the singlet
radical, and anion of the phenalenyl system, are listed in Table 1. by 364.4 kJ/mol at the 6-31G(d) level and by 81.1 kJ/mol at the
[Complete listings of the calculated vibrational frequencies can B3LYP level. The triplet is also more stable than the singlet for
be found in the supplementary data, Tables S1 (phenalenes) and 3aH-phenalene (3), by 341.2 kJ/mol with 6-31G(d) and by
S2 (phenalenyl system).] There were no signicant differences be- 60.3 kJ/mol with B3LYP. However, at the 6-31G(d) level of theory,
tween the RHF/6-31G* results from the PC Spartan Pro package and although the triplet of (3) is a stable minimum on the potential en-
the RHF/6-31G(d) results from Gaussian 98W; for consistency, ergy surface, the singlet of (3) optimizes as a transition state with a
however, only the Gaussian 98W results are reported herein. single imaginary frequency at 444.9 cm 1. All attempts to opti-
For 1H-phenalene (1), the singlet is more stable than the triplet mize this molecule so as to eliminate this imaginary frequency
by 125.5 kJ/mol with 6-31G(d), and by 208.4 kJ/mol with B3LYP. while maintaining the molecule as the desired isomer failed. This
The singlet is also more stable than the triplet for 9bH-phenalene frequency corresponds to the transfer of the hydrogen atom from
(4), by 83.8 kJ/mol with 6-31G(d) and by 22.7 kJ/mol with B3LYP. C3a to C1, i.e., the conversion of singlet (3) to singlet (1). In contrast,
All are stable minima on both the 6-31G(d) and the B3LYP poten- both the singlet and the triplet states of (3) are stable minima at
tial energy surfaces, with all real vibrational frequencies. The sin- the B3LYP level of theory. The triplet structures of (2) and (3) are
glet structures of (1) and (4) are illustrated in Fig. 2. illustrated in Fig. 3.

Table 1
The calculated properties for the isomers of phenalene and the phenalenyl system
1
Molecule Electronic energy (a.u.) Dipole moment (D) Selected vibrational frequencies (cm , uncorrected)
HF/6-31G(d) B3LYP/6-31G(d) HF/6-31G(d) B3LYP/6-31G(d) HF/6-31G(d) B3LYP/6-31G(d)
(1)-singlet 498.12312385 501.41464841 0.5857 0.6568 3179.2, 3197.8 [m(C1AH)] 2995.6, 3008.0 [m(C1AH)]
(1)-triplet 498.07513549 501.33529083 0.3065 0.5525 3153.6, 3167.1 [m(C1AH)] 2911.6, 2920.1 [m(C1AH)]
(2)-singlet 497.98971930 501.32717919 4.2957 3.1051 3133.9, 3150,5 [m(C2AH)] 2976.2, 2986.4 [m(C2AH)]
(2)-triplet 498.12850773 501.35806668 0.3736 0.5896 3127.5, 3130.5 [m(C2AH)] 2905.8, 2920.1 [m(C2AH)]
(3)-singlet 497.97090339 501.30871809 2.6875 2.0728 2798.0 [m(C3aAH)] 2736.2 [m(C3aAH)]
(3)-triplet 498.10084164 501.33169626 0.2343 0.3597 2962.2 [m(C3aAH)] 2714.3 [m(C3aAH)]
(4)-singlet 498.04215420 501.33607021 0.1345 0.1823 3047.4 [m(C9bAH)] 2810.4 [m(C9bAH)]
(4)-triplet 498.01024022 501.32741796 0.0188 0.0694 2818.0 [m(C9bAH)] 2727.4 [m(C9bAH)]
(5)-cation 497.34179328 500.58787202
(5)-radical 497.58376907 500.81065657 0.0000 0.0000
(5)-anion 497.52903049 500.84086927
52 J.M. Zoellner, R.W. Zoellner / Journal of Molecular Structure: THEOCHEM 863 (2008) 5054

The greater stability of the triplet state of (2) when compared to


. H
H
. H
H
(3) may be due to the structural potential for aromatic stabilization
within the systems [25]. As shown in Fig. 4, (2) can be represented
. . . as a naphthalene-type moiety fused to the ring containing the
diradical and the saturated carbon, while in (3), only a fused ben-
. H zene-type moiety can be produced, and that system is forced to be
locked into a single ring in (3). Thus (2), with the greater number of
(2) triplet ( 3) triplet aromatic resonance structures, is expected to be more stable than
(3), as is the case at both the HartreeFock and density functional
Fig. 4. The triplet ground states for (2) and (3) redrawn to represent some of the
levels of theory.
aromatic resonance structures possible for each isomer.
Selected structural parameters for the ground state phenalene
structures (1) and (4) as singlets and (2) and (3) as triplets
The electronic energies at the B3LYP/6-31G(d) level of theory are listed in Table 2. [Cartesian coordinates for all molecules can
indicate that for the ground state molecules, (1) singlet is the most be found in the supplementary data, Tables S3 (phenalenes) and
stable system, followed by (2) triplet, (4) singlet, and (3) triplet. S4 (phenalenyl system).] Singlet (1) and triplet (2) are nearly per-
Such an ordering might seem unusual in that the triplet system fectly planar molecules, with torsion angles exhibiting less than
of (2) is predicted to be signicantly (57.8 kJ/mol) more stable than 0.5 deviation from planarity, while triplet (3) and singlet (4) exhi-
the singlet system of (4). However, the structure of (4) may be con- bit signicant puckering at the nominally sp3-hybridized carbon
sidered as a perimeter of six conjugated carboncarbon double atom. Although all molecules were optimized without symmetry
bonds with a saturated carbon atom in the center, similar to constraints, (1) and (3) closely approximately Cs-symmetry, while
trans-15,16-dimethyl- and trans-15,16-diethyl-dihydropyrene, (2) and (4) approximate C2v- and C3v-symmetry, respectively.
molecules with two saturated carbon atoms surrounded by perim- Carboncarbon bond distances in the phenalenes are, on the
eters of seven conjugated carboncarbon double bonds [24]. In the whole, unremarkable, especially when considered in the context
dihydropyrene molecules, the perimeters are Hckel (4n + 2) 14 p- of the preceding discussion. The bond distances adjacent to the
electron aromatic systems, but in (4), the perimeter is formally a sp3-hybridized carbon atom are approximately 1.501.52 , as ex-
12 p-electron system and thus Hckel (4n) anti-aromatic (See pected for sp3sp2 CAC bonds. Little CAC bond alternation is ob-
Fig. 1). Thus, the synthesis of singlet (4) may not be quite as served in singlet (1) or triplet (2); both molecules appear to be
straight-forward as that of singlet (1). best described as naphthalene-like systems fused to a partially-sat-

Table 2
Selected calculated structural parameters for the ground state isomers of phenalene

Parameter 1H-phenalene (1) singlet 2H-phenalene (2) triplet 3aH-phenalene (3) triplet 9bH-phenalene (4) singlet
RHF/6-31G(d) B3LYP/6-31G(d) UHF/6-31G(d) B3LYP/6-31G(d) UHF/6-31G(d) B3LYP/6-31G(d) RHF/6-31G(d) B3LYP/6-31G(d)
r(C1AC2) 1.5026 1.5028 1.5007 1.4965 1.4133 1.4102 1.4675 1.4560
r(C2AC3) 1.3212 1.3402 1.5007 1.4965 1.3771 1.3713 1.3303 1.3545
r(C3AC3a) 1.4692 1.4599 1.3975 1.3953 1.5076 1.5068 1.4663 1.4550
r(C3aAC9b) 1.4318 1.4353 1.4422 1.4444 1.5172 1.5183 1.5176 1.5203
r(C9aAC9b) 1.4227 1.4252 1.4422 1.4444 1.4206 1.4161 1.5175 1.5204
r(C1AC9a) 1.5175 1.5194 1.3975 1.3953 1.4277 1.4323 1.3311 1.3559
r(C3aAC4) 1.3619 1.3840 1.4268 1.4245 1.5076 1.5068 1.3311 1.3558
r(C4AC5) 1.4163 1.4139 1.3951 1.3915 1.3771 1.3713 1.4675 1.4560
r(C5AC6) 1.3553 1.3751 1.3984 1.3927 1.4133 1.4102 1.3303 1.3545
r(C6AC6a) 1.4243 1.4239 1.4217 1.4219 1.4277 1.4323 1.4663 1.4552
r(C6aAC9b) 1.4085 1.4319 1.4264 1.4230 1.4206 1.4161 1.5175 1.5203
r(C6aAC7) 1.4154 1.4175 1.4217 1.4219 1.4203 1.4174 1.3311 1.3558
r(C7AC8) 1.3601 1.3777 1.3984 1.3927 1.3968 1.3927 1.4675 1.4560
r(C8AC9) 1.4096 1.4106 1.3951 1.3915 1.3968 1.3927 1.3303 1.3545
r(C9AC9a) 1.3654 1.3840 1.4268 1.4245 1.4203 1.4174 1.4663 1.4551
r(C1AH) 1.0886 1.1021 1.0765 1.0877 1.0755 1.0865 1.0763 1.0877
r(C2AH) 1.0766 1.0880 1.0926 1.1086 1.0761 1.0878 1.0756 1.0870
r(C3AH) 1.0763 1.0885 1.0765 1.0877 1.0760 1.0871 1.0758 1.0876
r(C3aAH) 1.1030 1.1228
r(C4AH) 1.0760 1.0878 1.0757 1.0872 1.0760 1.0871 1.0763 1.0877
r(C5AH) 1.0754 1.0868 1.0754 1.0870 1.0761 1.0878 1.0756 1.0870
r(C6AH) 1.0758 1.0875 1.0756 1.0869 1.0755 1.0865 1.0758 1.0876
r(C7AH) 1.0758 1.0875 1.0756 1.0869 1.0758 1.0872 1.0763 1.0877
r(C8AH) 1.0755 1.0870 1.0754 1.0870 1.0754 1.0869 1.0756 1.0870
r(C9AH) 1.0769 1.0884 1.0757 1.0872 1.0758 1.0872 1.0758 1.0876
r(C9bAH) 1.0997 1.1174
\(C9aAC1AC2) 114.2566 114.4968 123.2754 123.1645 120.8322 120.8030 121.4217 121.4225
\(C1AC2AC3) 123.3125 122.8069 113.1016 113.4846 121.2817 121.5356 121.4981 121.6249
\(C2AC3AC3a) 122.3414 122.4376 123.2754 123.1645 120.7740 120.6362 120.8492 121.0699
\(C3AC3aAC9b) 118.5466 118.6985 120.2574 120.2351 112.4220 112.9611 116.5539 116.8603
\(C3AC3aAC4) 121.7321 121.7670 121.4019 121.6788 114.6523 115.6094 123.3397 123.6879
\(C3aAC9bAC9a) 120.8922 120.9831 119.8329 119.7162 119.7652 119.6745 113.6822 114.6350
\(C9bAC9aAC1) 120.6434 120.5630 120.2573 120.2351 119.3236 119.3396 119.9951 119.3191
\(C2AC1AC9aAC9) 179.8583 178.9109 179.9745 179.9780 171.2475 170.3836 177.7793 177.0313
\(C3AC2AC1AC9a) 0.1559 1.3465 0.0549 0.0487 7.7943 8.3960 7.3372 5.8119
\(C3AC3aAC4AC5) 179.9697 179.5838 179.9975 179.9971 153.9432 154.8756 177.8037 179.9996
\(C3aAC9bAC9aAC9) 179.9466 179.7143 179.9915 179.9915 170.5768 172.0634 160.3170 161.4396
J.M. Zoellner, R.W. Zoellner / Journal of Molecular Structure: THEOCHEM 863 (2008) 5054 53

Table 3
Selected calculated structural parameters for the phenalenyl system

Parameter Phenalenyl (5) cation Phenalenyl (5) neutral radical 3aH-Phenalene (3) anion
RHF/6-31G(d) B3LYP/6-31G(d) UHF/6-31G(d) B3LYP/6-31G(d) RHF/6-31G(d) B3LYP/6-31G(d)
r(C1AC2) 1.3839 1.3938 1.3966 1.3926 1.3804 1.3919
r(C3AC3a) 1.4088 1.4170 1.4196 1.4185 1.4142 1.4216
r(C3aAC9b) 1.4110 1.4222 1.4305 1.4312 1.4347 1.4430
\(C1AC2AC3) 119.5424 119.8935 120.5745 120.7322 122.4100 121.7105
\(C2AC3AC3a) 121.2963 121.0738 120.7560 120.8072 120.1225 120.5206
\(C3AC3aAC9b) 118.9326 118.9810 118.9568 118.8241 118.6726 118.6212
\(C3aAC9bAC9a) 120.0000 119.9967 120.0000 120.0044 119.9998 120.0023
\(C2AC1AC9aAC9) 179.9994 179.9999 179.9998 179.9999 179.9996 179.9984
\(C3AC2AC1AC9a) 0.0002 0.0000 0.0003 0.0007 0.0000 0.0015
\(C3aAC9bAC9aAC9) 179.9995 179.9998 179.9997 179.9985 179.9996 179.9983

+,0,- 4. Conclusions

The four phenalene isomers, 1H-phenalene (1), 2H-phenalene


(2), 3aH-phenalene (3), and 9bH-phenalene (4), have been studied
computationally at both the HartreeFock 631G(d) and the den-
sity functional B3LYP/6-31G(d) levels of theory as both singlet
phenalenyl (5) and triplet state molecules. Both (1) and (4) are predicted to be
ground state singlets, while (2) and (3) are calculated to be ground
Fig. 5. A depiction of the phenalenyl system as a delocalized 12p-electron state triplets. While singlet (1), the only isomer synthesized to
surrounding a central carbon atom. date, is calculated to be the most stable, triplet (2) is also predicted
to be a potentially-synthesizable target. Singlet (4) may be best de-
scribed as an anti-aromatic 12 p-electron periphery of alternating
urated ring system containing the sp3-carbon atom at either C1 or
conjugated single and double bonds surrounding a central sp3-car-
C2, respectively. In a similar fashion, triplet (3) appears to be best
bon atom, while the phenalenyl cation, neutral radical, and anion
described as a benzene-like system fused to a two-ring system
appear to be composed of a delocalized 12 p-electron periphery
with an sp3-carbon atom at C3a.
surrounding a central carbon atom.
When compared to the other isomers of phenalene, (4)
exhibits signicant CAC bond alternation in the perimeter
Acknowledgements
carbon system that circles the central sp3-carbon atom at
C9b, with short bonds of approximately 1.35 alternating
The authors acknowledge the National Science Foundations
with longer bonds of approximately 1.46 . Such a calculated
Course, Curriculum, and Laboratory Improvement Program, Adap-
structure highlights the potentially anti-aromatic character of
tation and Implementation Section (NSF-9950344) for generous
the molecule and underscores the description of the mole-
support for the initial purchase of computers and computational
cule as a 12 p-electron perimeter surrounding the central
chemistry software. Matching funds and additional support have
carbon atom.
been received from the Humboldt State University Department of
In contrast to the signicant structural differences observed in
Chemistry, the College of Natural Resources and Sciences, the Of-
the isomers of phenalene, the structures (Table 3) of the phenale-
ce for Research and Graduate Studies, the Ofce of the Vice-Pres-
nyl cation, neutral radical, and anion (5) are very similar, being
ident for Academic Affairs, and the Ofce of the President, as well
nearly exactly planar (torsion angles with less than 0.001 devia-
as from the Humboldt State University Sponsored Programs Foun-
tion from planarity) and exhibiting nearly perfect D3h symmetry.
dation. One of us (J.M.Z.) also acknowledges the receipt of a Hum-
No bond alternation is observed. However, at the B3LYP/6-31G(d)
boldt Chemistry Clark Research Scholarship.
level of theory, some trends in bond lengths can be noted: When
comparing, in order, the cation, neutral radical, and anion of the
phenalenyl system, C1AC2 is observed to shorten slightly, C3AC3a Appendix A. Supplementary data
to lengthen slightly, and C3aAC9b to lengthen to a somewhat great-
er extent as the charge on the system changes from positive to Supplementary data associated with this article can be found, in
neutral to negative. the online version, at doi:10.1016/j.theochem.2008.05.017.
The phenalenyl cation, neutral radical, and anion each appear
to be best described as a delocalized 12 p-electron periphery sur- References
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