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Titel: Peri-tetracene Diradicaloid

Autoren: Jishan Wu, Yong Ni, Tullimilli Y. Gopalakrishna, Hoa Phan,

Tun Seng Herng, Shaofei Wu, Yi Han, and Jun Ding

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Zitierweise: Angew. Chem. Int. Ed. 10.1002/anie.201804276

Angew. Chem. 10.1002/ange.201804276

Link zur VoR: http://dx.doi.org/10.1002/anie.201804276

http://dx.doi.org/10.1002/ange.201804276
Angewandte Chemie 10.1002/ange.201804276

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Peri-tetracene Diradicaloid
Yong Ni,[a] Tullimilli Y. Gopalakrishna,[a] Hoa Phan,[a] Tun Seng Herng,[b] Shaofei Wu,[a] Yi Han,[a] Jun
Ding,[b] and Jishan Wu*[a]
Abstract: Peri-acenes are good model compounds for zigzag
graphene nanoribbons but their synthesis is extremely challenging
due to their intrinsic open-shell diradical character. Herein we report
the successful synthesis and isolation of a stable peri-tetracene
derivative PT-2ClPh in which four 2,6-dichlorophenyl groups are
attached onto the most reactive sites along the zigzag edges. The
bisanthene, the teranthene and quarteranthene derivatives, and
both exhibited interesting open-shell diradical character.8 The
synthesis of the laterally extended bisanthene molecules, the
peri-tetracene and peri-pentacene turned out to be a very
challenging task. Our group initialized the synthesis9 and a few
other groups worked along the same way,10 but all the attempts

Accepted Manuscript
structure was confirmed by X-ray crystallographic analysis and its on this synthesis failed. The major challenges are the lack of an
electronic properties were systematically investigated by both efficient intramolecular cyclization method to construct the
experiments and theoretical calculations. It exhibits open-shell singlet framework and the intrinsic high reactivity of both molecules. Our
ground state with a moderate diradical character (y0 = 51.5% by spin-unrestricted DFT calculations (UB3LYP/6-31G(d,p)) predict
calculation) and a small singlet-triplet gap (ES-T = -2.5 kcal/mol by that the parent bisanthene has a closed-shell ground state, while
SQUID measurement). It displays global aromatic character, which is the peri-tetracene and peri-pentacene have open-shell singlet
different from the smaller-size bisanthene analogue BA-CF3. ground state (Table S1 in the Supporting Information (SI)). The
SOMO-α and SOMO-β show disjoint feature with the α/β spins
localized at the two zigzag edges (Figure 1b-c). Accordingly, the
Zigzag graphene nanoribbons (ZGNRs) are predicted to be
spin densities are mainly distributed onto the zigzag edges,
metallic and have promising applications in nanoelectronics and
implying high reactivity at these sites. Natural orbital occupation
spintronics.1 However, chemical synthesis of this type of
number (NOON) calculations (UCAM-B3LYP/6-31G(d,p)) give a
graphene nanoribbon is extremely challenging due to their
diradical character (y0) of 52.5% and 75.4% for peri-tetracene and
intrinsic high reactivity, which is related to their (nearly) zero band
peri-pentacene, respectively. Therefore, to synthesize a stable
gap and polyradical character.2 Chemists have been looking into
derivative, it is necessary to kinetically block the reactive zigzag
their small-size model compounds for a long time. Among them,
edges by appropriate substituents and to develop an innovative
acenes represent the smallest series of ZGNR molecules,3 and
strategy to build up the framework. After almost 10 years of effort,
theoretical studies predicted that long acenes from hexacene
we eventually synthesized a stable peri-tetracene derivative PT-
onward would exhibit open-shell diradical character and be highly
2ClPh (Scheme 1) in crystalline form. Four bulky and electron-
reactive.4 So far, the longest persistent acene molecule can be
withdrawing 2,6-dichlorophenyl groups are attached onto the
obtained by wet chemistry is a nonacene derivative reported by
most reactive sites at the two zigzag edges allow sufficient
Anthony et al..5 Another type of ZGNR model compounds are the
stability and solubility for physical characterization.
peri-fused acenes, the so-called peri-acenes (Figure 1a). Based
on the acene units fused, the molecules are called as bisanthene,
peri-tetracene, peri-pentacene, and so on. A common feature of
these molecules is that an open-shell diradical form can be drawn,
accompanying with recovery of two additional aromatic sextet
rings (hexagons shaded in blue, Figure 1a). The gained aromatic
stabilizing energy may partially compensate the energy required
to break a C(sp2)-C(sp2) π-bond to form a diradical, resulting in a
possible diradical character, especially for the long homologs.6
The smallest member, the bisanthene, is known to be a reactive
species, and our group and others have developed various
methods to make soluble and stable bisanthene derivatives since
2009.7 All the bisanthene compounds reported so far have
displayed closed-shell ground state, with prominent fluorescence.
On the other hand, Kubo’s group developed vertically extended

[a] D. Y. Ni, Dr. T. Y. Gopalakrishna, Dr. H. Phan, S. Wu, Y. Han, Prof.

J. Wu
Department of Chemistry, National University of Singapore
3 Science Drive 3, 117543, Singapore
Fax: (+65) 6779 1691
E-mail: chmwuj@nus.edu.sg
[b] Dr. T. S. Herng, Prof. J. Ding
Department of Materials Science and Engineering, National
University of Singapore, 119260, Singapore Figure 1. (a) Representative closed-shell and open-shell diradical resonance
forms of peri-acenes. Calculated (UB3LYP/6-31G(d,p)) spin-α and spin-β
Supporting information for this article is given via a link at the end of profiles and the spin density distribution maps of the singlet diradical forms of
the document. peri-tetracene (b) and peri-pentacene (c).

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Previous attempted syntheses mainly included two
strategies: (a) synthesis of singly linked or partially fused acene
dimers followed by intramolecular ring cyclization,9a,10c and (b)
synthesis of fused peri-acene quinones followed by nucleophilic
addition/reductive aromatization.9b,10b The first method suffered
from the poor stability of the dimers while the second approach
was limited by the poor solubility as well as undesirable Michael
addition. Our new strategy was based on intramolecular Friedel-
Crafts cyclization followed by oxidation (Scheme 1). Sonogashira
coupling between 1 and 2 gave the dibromide 3, which underwent
Suzuki coupling with biphenyl-2-boronic acid to afford 4. Iodine
monochloride (ICl) mediated cyclization gave the diiodo-
compound 5, which underwent oxidative cyclization with 2,3-
dichloro-5,6-dicyano-p-benzoquinone (DDQ) in the presence of
trifluoromethanesulfonic acid (TMSA) to generate 6. The structure
of 6 was confirmed by single-crystal analysis (see SI). Due to the
severe steric repulsion between the C-I bonds and the
neighboring benzene rings, the backbone is highly distorted.
Nevertheless, lithiation of 6 with n-BuLi proceeds and subsequent
quenching with 2,6-dichlorobenzaldehyde gave the diol 7, which
was confirmed by X-ray analysis again (see SI). Intramolecular
Friedel-Craft cyclization mediated by TMSA provided the dihydro-
compound 8 and its syn stereoisomer was confirmed by X-ray
analysis (see SI). However, oxidative dehydrogenation of 8 with
various oxidants (e.g., DDQ) did not proceed, presumably due to
the strong electron-withdrawing nature of the substituent.
Fortunately, 8 can be deprotonated with KOBut to give the dianion,
which was in situ oxidized by p-chloranil to give the final product
PT-2ClPh in 88% yield. PT-2ClPh was sensitive to silica gel but
can be purified by Bio-beads column followed by crystallization in
cooled toluene solution. Its half lifetime in THF under ambient air
and light conditions is about 7 hours as monitored by absorption
spectroscopy (Figure S1).
Scheme 1. Synthetic route of the PT-2ChPh: (a) Pd(PPh3)2Cl2, CuI, Et3N, rt;
(b) biphenyl-2-boronic acid, Pd(PPh3)4, K2CO3, toluene/H2O, reflux, overnight;
(c) ICl, DCM, -78 oC, 2h; (d) 2.2 eq DDQ, TMSA, DCM, -78 oC, 5h; (e) i) n-BuLi,
THF, -78 oC, 2h; ii) 2,6-dichlorobenzaldehyde, rt, 5h; (f) TMSA, DCM, rt, 2 h; (g)
KOBut, THF, rt, 5h; (h) p-chloranil, THF, rt, 30 minutes. The chemical structure
of a bisanthene derivative BA-CF3 is also shown.
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10.1002/ange.201804276
X-ray crystallographic analysis confirmed the structure of
PT-2ClPh.11 Due to the steric repulsion between the neighboring
2,6-dichlorophenyl substituents, the backbone was slightly
deviated from planarity and the substituents are almost
perpendicular to the backbone (Figure 2a). Bond length analysis
was performed for the backbone of PT-2ClPh and compared with
that of our previously reported meso- substituted bisanthene
compound BA-CF3 (see structure in Scheme 1).7d It was found
that the bonds a/b (1.467/1.447 Å) linking the two anthracene
units in BA-CF3 were significantly shortened in PT-2ClPh (bonds
a’/b’, 1.459/1.442 Å) (Figure 2b), indicating enhanced electronic
coupling between two tetracene units and increased contribution
Accepted Manuscript
of the diradical form (Figure 1a). The bond length alternation in
each hexagon rings of the top/bottom anthracene/tetracene units
is small, implying an aromatic character. Indeed, nucleus
independent chemical shift (NICS)12 calculations gave negative
NICS(1)zz values, and the outmost benzenoid rings are more
aromatic (more negative NICS(1)zz values). The six-membered
rings linking the two anthracene units show positive NICS(1)zz
values (+12.6 ppm) in BA-CF3, which become less positive in PT-
2ClPh (Figure 2b), implying a stronger electronic interaction in
the latter.
Figure 2. (a) X-ray crystallographic structures of the PT-2ClPh (left: top view,
right: side view); (b) selected bond lengths of the backbone of BA-CF3 and PT-
2ClPh (in Å). The red numbers in the hexagons are calculated NICS(1)zz values.
Anisotropy of the induced current-density (ACID)13 and iso-
chemical shielding surface (ICSS)14 calculations (UB3LYP/6-
31G(d,p)) were carried out for parent bisanthene and peri-
tetracene to further understand the electronic structure and
aromaticity. Interestingly, the ACID plot of the bisanthene shows
two nearly isolated clockwise current flow circuits at the two
anthracene units (Figure 3a and more magnified images in SI),
indicating that the two aromatic anthracene units are indeed
weakly coupled. On the other hand, the π electrons in peri-
tetracene are mainly delocalized along the periphery with a
Angewandte Chemie 10.1002/ange.201804276

COMMUNICATION
clockwise current flow. This means that the molecule is globally
aromatic and the two tetracene units are coupled each other,
which is consistent with the bond length analysis. Similarly, the
two-dimensional ICSS map of bisanthene revealed two isolated
(Figure S3) and its dianion was obtained by deprotonation of
compound 8 with KOBut in THF, giving an intense absorption
band at λmax = 934 nm (Figure S2).

342
12
aromatic anthracene units with the two bridging hexagons in a BA-CF3

362
292
PT-2ClPh
strongly de-shielded (negative ICSS(1)zz values) chemical 10
environment (Figure 3b). For peri-tetracene, the outmost four

 / 104 M-1 cm-1

benzene rings are more aromatic, and the central bridging 8

683
hexagon is almost non-aromatic. All the crystallographic data and
6

872
calculations suggest a fundamental change of the electronic

413
structure for the long peri-acenes. 4

(a)

1010
580

Accepted Manuscript
2

0
300 400 500 600 700 800 900 1000 1100 1200 1300

Wavelength (nm)

0.65
+

Current

0.16
(b)
+

-1.49
+
+

-1.15
y axis

-1.6 -1.2 -0.8 -0.4 0.0 0.4 0.8

Potential (V) vs Fc/Fc+

x axis x axis
Figure 3. (a) Calculated ACID plots of parent bisanthene and peritetracene
(isovalue: 0.015). The magnetic field is perpendicular to the XY plane and points
out through the paper. (b) Calculated 2D ICSS maps of the parent bisanthene
and peri-tetracene at the XY plane.
Compound PT-2ClPh in DCM shows a major absorption
band in the near-infrared (NIR) region with maximum (max) at 872
nm, along with a shoulder at 1010 nm (Figure 4a). For comparison,
the closed-shell BA-CF3 exhibits a typical well-resolved p-band
at max = 683 nm. The appearance of an additional long-
wavelength shoulder for PT-2ClPh is strong indication that it has
open-shell singlet diradical ground state, and the band is believed
to originate from the H, H → L, L double excitation (H: HOMO; L:
LUMO).15 The optical energy gap of PT-2ClPh and BA-CF3 was
estimated to be 1.12 eV and 1.74 eV, respectively, from the lowest
energy absorption onset. Time-dependent DFT calculations on
PT-2ClPh suggest that the band at 872 nm is ascribed to the H→L
electronic transition, and the bands at the higher energy (max =
342 nm) are due to a combination of multiple H-n→L+m
(n,m=0,1,2) electronic transitions (see SI).
Compound PT-2ClPh showed two reversible oxidation
waves with half-wave potential E1/2ox at 0.16 and 0.65 V, and two
reduction waves with half-wave potential E1/2red at -1.15 and -1.49
V (vs Fc+/Fc) (Figure 4b). The HOMO and LUMO energy level
was estimated to be 4.87 eV and 3.75 eV from the onset of the
first oxidation and reduction wave, respectively. The
electrochemical energy gap was determined to be 1.12 eV, which
is in consistent with the optical energy gap. Compound PT-2ClPh
can be chemically oxidized into its radical cation form with
NO•SbF6 in dry DCM, showing an intense electronic absorption
band in the NIR region (λmax = 1148 nm) and strong ESR signal
Figure 4. (a) UV-Vis-NIR absorption spectra of BA-CF3 and PT-2ClPh in DCM
(c = 2×10-5 M) at room temperature. (b) Cyclic voltammogram of PT-2ClPh in
DCM with 0.1 M Bu4N•PF6 as supporting electrode, at a scan rate of 50 mVs-1.
The 1H NMR spectrum of PT-2ClPh in THF-d8 was
significantly broadened at room temperature, and cooling of the
solution down to 178 K resulted in partially resolved spectrum,
which can be assigned to the desired structure with assistance of
2D COSY NMR technique (Figures S4-S5). This is a strong
evidence that PT-2ClPh indeed has open-shell singlet ground
state and the NMR broadening is due to the thermal population of
triplet diradical species at elevated temperatures, a common
phenomenon for many recently reported open-shell singlet
diradicaloids and polyradicaloids.16 To further support it, NOON
calculations (UCAM-B3LYP/6-31G(d,p)) predicted a diradical
character of 51.5%. PT-2ClPh in THF showed a five-line ESR
signal (Figure 5a), which can be well simulated based on the
calculated spin density distribution (inset in Figure 5b) and
hyperfine coupling constants (Figure S6). The ESR intensity
decreased with the lowering of temperature, and fitting of the data
in frozen solution by using Bleaney−Bowers equation17 gave a
singlet-triplet energy gap (ES-T) of -2.4 kcal/mol (Figure S7).
Alternatively, superconducting quantum interference device
(SQUID) measurement was conducted for the microcrystalline
sample of PT-2ClPh at 2-300 K (Figure 5b). Similar to variable-
temperature ESR measurements, the product of the molar
magnetic susceptibility (χM) and temperature (T) increased after
100 K and fitting of the data using Bleaney−Bowers equation gave
a singlet-triplet energy gap ∆ES-T of −2.5 kcal/mol. Therefore,
compound PT-2ClPh was unambiguously confirmed to be an
open-shell singlet diradicaloid with a small optical/electrochemcial
band gap and a small singlet-triplet energy gap.

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Accepted Manuscript
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M·T (emu·K·mol-1)

0.06
0.04
0.02
0.00
0 50 100 150 200 250 300
Temperature (K)
Figure 5. (a) Experimental and simulated ESR spectra of PT-2ClPh in THF at
298 K; (b) χMT–T plot in the SQUID measurement of the microcrystalline PT-
2ClPh. The solid line is the fitting curve according to Bleaney-Bowers equation
and inset is the calculated spin density distribution of the triplet diradical form.
In summary, a stable peri-tetracene derivative PT-2ClPh was
obtained by using a new synthetic strategy.18 It was reasonably
stable due to the proper blocking of the most reactive sites at the
two zigzag edges by the bulky and electron-withdrawing 2,6-
dichlorophenyl groups. Analysis shows that it exhibits open-shell
diradical character with a small singlet-triplet excitation energy. It
has a small energy gap and shows characteristic absorption of
open-shell singlet diradicaloid in the NIR region. It also displays
global aromatic character that is different from the bisanthene.
Our synthetic method and physical studies shed some light on the
development of even larger size peri-acene molecules or other
zigzag edged nanographenes.
Acknowledgements
J. W. acknowledges financial support from the Tier 3 programme
(MOE2014-T3-1-004). We thank Dr. Tan Geok Kheng for the X-
ray analysis and Dr. Ng Chee Koon for assistance on VT NMR
measurement.
Keywords: polycyclic aromatic hydrocarbon • diradicaloid • peri-
acene • acene • zigzag edge
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Entry for the Table of Contents (Please choose one layout)

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Synthesis of peri-tetracene done. A Y. Ni, T. Y. Gopalakrishna, H. Phan, T.
stable peri-tetracene derivative was S. Herng, S. Wu. Y. Han, J. Ding, and J.
obtained in crystalline form. It has Wu*
open-shell singlet ground state with a
moderate diradical character. It shows Page No. – Page No.
amphoteric redox behaviour with a
Peri-tetracene Diradicaloid

Accepted Manuscript
small optical and electrochemical
energy gap. It is magnetically active
and exhibits a small singlet-triplet
excitation energy. It is globally
aromatic.

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