Nonlinear Polyfused Aromatics with Extended -Conjugation from Phenanthrotriphenylene, Tetracene, and Pentacene: Syntheses, Crystal Packings, and Properties

Article abstract of DOI:10.1021/acs.joc.8b01582

New classes of nonlinear polyaromatics with extended conjugation at lateral and longitudinal directions from triphenylene, tetracene, and pentacene backbones are reported. These planar and twisted polyfused aromatics are obtained through specific and selective multifold Scholl reactions from predesigned polyaryls. These derivatives displayed shifted or perfect cofacial packing motifs. Single crystals of one derivative, phenanthro[9,10:b]triphenylene, were used as p-channel materials in fabricating transistor devices, which exhibited an average mobility of 0.38 cm² V^-1 s^-1 and a maximum mobility reaching 1.15 cm² V^-1 s^-1.

Full text of DOI:10.1021/acs.joc.8b01582

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Article
Non-linear Polyfused Aromatics with Extended #–
Conjugation from Phenanthrotriphenylene, Tetracene and
Pentacene: Syntheses, Crystal Packings, and Properties
Sushil Kumar, Ding-Chi Huang, Samala Venkateswarlu, and Yu-Tai Tao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01582 • Publication Date (Web): 24 Aug 2018
Downloaded from http://pubs.acs.org on August 24, 2018
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Page 1 of 32
The Journal of Organic Chemistry
Nonꢀlinear Polyfused Aromatics with Extended π–Conjugation from
Phenanthrotriphenylene, Tetracene and Pentacene: Syntheses, Crystal Packings, and
Properties
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Sushil Kumar,a DingꢀChi Huang,a Samala Venkateswarlu, a,b,c and YuꢀTai Taoa,*
9
b
aInstitute of Chemistry, Academia Sinica, Taipei, Taiwan, 115. Taiwan International
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Graduate Program, Sustainable Chemical Science and Technology, Academia Sinica,
c
Taipei, Taiwan, Department of Applied Chemistry, National Chiao Tung University,
Hsinchu, Taiwan
Supporting Information (SI) Placeholder
Abstract New classes of nonꢀlinear polyaromatics with extended conjugation at lateral
and longitudinal directions from triphenylene, tetracene and pentacene backbones are
reported. These planar and twisted polyfused aromatics are obtained through specific and
selective multifold Scholl reactions from preꢀdesigned polyaryls. These derivatives
displayed shifted to perfect cofacial packing motifs. Singleꢀcrystals of one derivative,
phenanthro[9,10:b]triphenylene, were used as p–channel materials in fabricating transistor
devices, which exhibited an average mobility of 0.38 cm2Vꢀ1sꢀ1 and a maximum mobility
reaching 1.15 cm2Vꢀ1sꢀ1
Introduction
The polycyclic aromatic hydrocarbons (PAHs), with variable modes of ring fusion,
molecular shapes and geometry, have always attracted researchers’ attention because the
rich properties they possess, which find wide applications in many electronic and
optoelectronic devices.1 The packing motifs of a PAH in the solid or film state is crucial to
its properties, such as photoluminescence, electronic coupling, and charge mobility.2
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Depending on the π–electron distribution and geometric requirement, the polyaromatics
may adopt cofacial, herringbone, or shifted π–stacking arrangement, each with different
impact on their π–π electronic couplings and thus charge transport rate.3 Extended
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conjugation system is generally favored for greater chance of π–π stacking and narrower
band gap. Linear acenes such as anthracene, tetracene, pentacene, and hexacene are typical
examples with the electronic coupling and thus charge mobility scales with the dimension
of conjugation.4
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Linear acenes are known to crystallize in herringbone arrangements.5 Expanding the
conjugation from the linear acenes in other dimensions is of interest in that new packing
motifs and new intermolecular interactions may develop and lead to new or different
possibilities in many physical or electronic properties.6 To access these extended acenes,
Bergmann and others were successful in synthesizing the parent phenanthrotriphenylene
from respective polyaryl and other substrates.7 Recently, we reported the syntheses of
some polyaromatics with π–conjugation expanded/extended from coronene, perylene and
pyrene core frameworks and some of them were shown to exhibit good hole carrier
mobility in fieldꢀeffect transistor configuration.8
In this work, we demonstrate the synthesis and characterization of a series of twisted or
planar PAHs extended from phenanthrotriphenylene, tetracene and pentacene frameworks.
These derivatives were obtained by carrying out Scholl reactions on respective 1,2,4,5ꢀ
tetraaryl substituted benzenes. The Scholl reactions of these polyaryls incorporating larger
aromatic units such as 1ꢀnaphthyl, 2ꢀnaphthyl, 2ꢀanthracenyl groups exhibited different
reactivity and regioselectivity in the annulation steps. The resultant PAHs display a range
of crystal packings, from exactly cofacial to shifted πꢀstacking, to herringbone
arrangements, depending on the substitution and shape of the molecule. Single crystalꢀ
based fieldꢀeffect transistor device with one of them, phenanthro[9,10:b]triphenylene, gave
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a maximum hole mobility of 1.15 cm2Vꢀ1sꢀ1and an average mobility of 0.38 cm2Vꢀ1sꢀ1,
which was higher than that measured for known triphenylenes and
phenanthrotriphenylenes,9 demonstrating the potential of these molecules as
semiconducting materials.
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Results and Discussions
Syntheses
The syntheses of the PAHs (T1–T16) reported here all started from the tetraarylꢀ
substituted benzene derivatives and are illustrated in the Schemes 1–4, with the
preparation of starting polyaryls P1–16 shown in the Schemes S1ꢀS4 (Supporting
Information, SI). The polaryls of this type have been interesting scaffolds to undergo
Scholl reaction and other cyclodehydrogenation reactions, furnishing polyaromatic
hydrocarbons with grapheneꢀtype architectures.10 With appropriate aryl substitution,
expansion of conjugation in longitudinal or lateral direction of acenes can be envisaged.
Various reagents, such as FeCl3, DDQ, MoCl5, AlCl3, and AlBr3 are known to be used in
effecting cyclodehydrogenations.11 Among these, we used FeCl3 as the catalyst in the
Scholl reactions presented here.
R1
R1
reaction
T1: R1 = H (82%)
R
R
R
R
T2:
T3:
conditions:
FeCl3/DCM
MeNO2,
R1 = Me (86%)
R1 = F (78%)
T4
: R1 = Cl (77%)
T5: R1 = OMe (93%)
4−48 h, rt
P1: R = phenyl
P2: R = 4-fluorophenyl
P3
R1
R1
: R = 4-chlorophenyl
P4:
P5:
R = 4-tolyl
R = 4-methoxyphenyl
Scheme 1. Synthesis of substituted phenanthrotriphenylenes (T1–T5).
Scheme 1 shows the Scholl reactions of benzene with 1,2,4,5ꢀpositions substituted with
the same four groups of paraꢀsubstituted phenyls, which is the most studied scaffolds.
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Thus the polyaryls P1–P5, carrying different paraꢀsubstituents, exhibited different
reactivity (reaction time from 4 h to 48 h), resulted in different yields (72% to 93%). Here,
the paraꢀfluoro and paraꢀchlorophenylꢀsubstituted polyaryls had lower reactivity than that
of the unsubstituted and paraꢀmethoxyꢀsubstituted ones, presumably because the oxidative
formation of cation radical in the reaction mechanism is disfavored by electronꢀ
withdrawing groups.
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Scheme 2 shows the Scholl reactions of polyaryls with the same yet larger naphthyl or
anthracenyl units at all four positions. These polyaryls in general showed higher reactivity
than with substituted phenyls (except for methoxyꢀsubstituted one), possibly because these
involved more stable reaction intermediates, according to the reported reaction
mechanism.12 However, with different R groups of 2ꢀnaphthyl, 1ꢀnaphthyl and 2ꢀ
anthracenyl, the annulating pattern varied. With 1ꢀnaphthyl unit, the only possible position
of annulation would be the nearby 2ꢀposition, which was indeed the observed reaction
site.13 However, as shown in Scheme 2, the annulation occurred together with chlorination
at 4ꢀposition to give the derivative T7. No parent compound was found.
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1
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T6
(81%)
4
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8
9
R
= naphtha
len-2-yl
Cl
Cl
Cl
R
= naphtha
len-1-yl
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R
R
R
R
P6:
R = naphthalen-2-yl
P7: R = naphthalen-1-yl
P8: R = anthracen-2-yl
T6a
Cl
T7 (72%)
R
= Anthra
cen-2-yl
reaction
conditions:
FeCl3/DCM
MeNO2,
12−36 h, rt
T8
Scheme 2. Synthesis of tetranaphtho pentacenes (T6) and tetrabenzo
phenanthrotriphenylene (T7).
This led to extension in the longitudinal direction from the phenanthrotriphenylene
framework. With 2ꢀnaphtyl groups, the annulation occurred selectively at the 1ꢀposition of
the naphthyl units, followed by further annulation at the 8ꢀposition to give T6, which has a
pentaceneꢀcored framework. The other mode of annulation at the 3ꢀposition was not
observed. The regioselectivity is presumably due to the stability of a benzylic cation
involved in the reaction mechanism (Scheme S5, SI). For 2ꢀanthracenylꢀsubstituted one,
the precursor was sparingly soluble and no expected annulation product T8 was isolated,
although the annulation at the 1ꢀposition seems plausible.
Scheme 3 shows the Scholl reactions with benzene substituted with two types of groups,
from phenyl, naphthyl, and anthracenyl groups substituted unsymmetrically around
benzene ring. Again, whenever 1ꢀnaphthyl group or phenyl group was involved, the
neighboring 2ꢀposition was where the annulation occurred. While with 2ꢀnaphthyl group
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or 2ꢀanthracenyl group involved, the 1ꢀposition was where the annulation occurred. Thus
regioselective formation of T9–T13 was obtained (Scheme 3), with chlorination occurred
on the 10ꢀposition of anthracene unit in T13. The observed regioselectivities for T7 and
T13 are rationalized by the electronic effect on the stability of the intermediates involved
(Schemes S6 and S7, SI).
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Cl
T13 (76%)
Cl
R
1 = phenyl
R
1 = naptha
len-1-yl
R2 = anthra
Cl
cen-2-yl
R2 = naptha
len-2-yl
R1
R2
R2
R1
P9:
R1 = phenyl, R2 = 4-fluorophenyl
T13a
T12 (90%)
P10: R1 = phenyl, R2 = naphthalen-2-yl
P11: R1 = 4-tolyl, R2 = naphthalen-2-yl
Cl
P12:
P13:
R1 = naphthalen-1-yl, R2 = naphthalen-2-yl
R1 = phenyl, R2 = anthracen-2-yl
R
1 = phenyl
R
1 = phenyl and 4-tolyl
R2 = 4-fluorophenyl
R2 = naphtha
F
len-2-yl
R
reaction
conditions:
FeCl3/DCM
MeNO2,
F
T9
6−36 h, rt
(82%)
R
R = H (84%)
R = Me (88%)
T10:
T11:
Scheme 3. Synthesis of phenanthrotriphenylenes (T9–T13).
Scheme 4 shows additional reactions for benzene substituted with different aryl groups on
each side of the benzene ring. In cases where 2ꢀnaphthyl substituent was involved,
multifold oxidative annulations at the 1,8ꢀpositions, yielding T14, T16 (Scheme 4), were
obtained. These are derivatives with a π–expansion from tetracene framework.
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R1 = phenyl
R2 = 4-fluoro
R
-2-yl
R2 = phenyl
1 = naphthalen
phenyl
R1
R1
R1
R2
F
T15
(86%)
P15: R1 = phenyl, R2 = 4-fluorophenyl
P16:
T16
reaction
(86%)
R1 = 2-naphthyl, R2 = phenyl
conditions:
FeCl3/DCM
MeNO2,
6−24 h, rt
Scheme 4. Synthesis of phenanthrotriphenylenes and tetracenes derivatives (T14–T16).
Singleꢀcrystal Xꢀray analyses
To obtain the information about the packing motif, singleꢀcrystals of these PAHs were
grown by physical vapor transport method (PVT). PVT method produced colorless, lightꢀ
yellow to yellow and redꢀcolored singleꢀcrystals of phenanthrotriphenylenes, tetracenes
and pentacenes derivatives, with which the singleꢀcrystal X–ray measurements were
performed (Figure S63, SI). Crystal packing of polyaromatics has been widely studied and
broadly classified into categories such as herringbone, sandwich, γ, and β types, according
to their balance of C⋅⋅⋅C and C⋅⋅⋅H interactions.14 Of the seven crystals shown in Figure 1,
T1 and T6, which were planar molecules, adopting γ type packing, with the neighboring
molecules parallel, yet shifted (glided) to each other.
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(b)
T1
(a)
T1
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(d)
(f)
T10
T13
(c)
(e)
T10
T13
(h)
(j)
T7
(g)
(i)
T7
T12
T12
(l)
T14
T6
(k)
T14
T6
(n)
(m)
Figure 1. π–π stacks and packing motif of designed PAHs.
The two columns of cofacially πꢀstacked layers were separated by another layer, whose πꢀ
face made an angle with the πꢀfaces of neighboring layers (with a dihedral angles of 62°
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and 65° in T1 and T6, respectively). The triphenylene and tetranaphthopentacene units had
a π–π coupling distance of ~3.4 Å between the neighboring ring planes (Figure 1a and 1m).
The rest of the molecules are contorted, with various extent of twist of the molecules. In
the slightly twisted T10, the packing motif was somewhat perturbed to one with poorer π–
π cofacial overlap and longer coupling distance of 3.7 Å in the triphenylene units of
neighbouring molecules. The much twisted and chlorinated derivatives T7 and T13 exhibit
nearly perfectly cofacial overlap, from which a stronger electronic coupling can be
expected. In contrast to T10, the multiple chlorine atoms in these two molecules may have
strong Cl⋅⋅⋅Cl interactions15 and draw the neighbouring molecules face to face to have
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more C⋅⋅⋅C (~3.4 Å) and CCl⋅⋅⋅HC (2.8 Å to 2.9 Å) contacts (Figure S65, SI). The
polyfused frameworks of T14 (a twist angle of 35° between the naphthyl moiety and the
central tetracene unit) and T12 (twist angles 12° and 33° between the two naphthyls and the
central anthracene unit) were more twisted compared to other derivatives, they also had
good faceꢀtoꢀface overlap (β type), in which two cofacial layers were separated by 3.3 Å.
In derivative T14, π–π stacked molecular layers were also nearly cofacial with each other.
The diverse geometry of these PAHs, as it affected their packing, could contribute to their
optical profiles as well.
Photophysical studies
These PAHs exhibited white (substituted phenanthrotriphenylenes), lightꢀyellow to yellow
(phenanthrotriphenylenes with larger frameworks), brown to red colors (benzo and
naphthotetracenes and pentacenes) in their solid states. The electronic absorption spectra
of the phenanthrotriphenylenes and naphthopentacenes are sketched in the Figures 2 and
S66 (SI), while the related data is enclosed in Table S1 (SI). The electronic absorption of
triphenylene framework was shown to be in the region of 200 to 280 nm.16
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1.2
0.9
0.6
0.3
0.0
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4
5
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8
T1
(a)
T2
T3
T4
T5
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250
300
350
400
450
500
wavelength (nm)
1.2
0.9
0.6
0.3
0.0
T1
(b)
T10
T12
T13
250 300 350 400 450 500 550
wavelength (nm)
Figure 2. Normalized absorption spectra of phenanthrotriphenylenes as recorded in
dichloromethane.
As theoretically suggested from the Clar’s rule,17 the absorption bands of
phenanthrotriphenylenes were expected to be derived from triphenylene portion. The
absorption features of parent phenanthrotriphenylenes followed the similar pattern for
triphenylenes. The absorption bands of substituted phenanthrotriphenylenes such as T2–
T5 were found to arrange in the order of the electronic effects mediated by methoxy,
methyl groups, fluorine and chlorine atoms. With their effective π–conjugating ability, the
large phenanthrotriphenylenes such as T10, T12, T7 and T13 shifted their absorption
maxima to longer wavelength. The tetracene derivatives T14 and T16 showed
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characteristic absorption pattern of tetracene unit,18 although there was a bathochromic
shift in their absorption profiles (Figure S66, SI).
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HOMOꢀLUMO Energies
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9
The energies of highest occupied molecular orbitals (EHOMO) for selected PAHs were
measured by photoelectron spectrometry (ACꢀ2) from the solid samples of PAHs. The
optical band gaps of these PAHs were estimated from the absorption edges of their
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UV−visible spectra and the energies of lowest unoccupied molecular orbitals (ELUMO
)
were calculated by subtracting the optical band gap from the HOMO energies. The
HOMO and LUMO energies are given in the Table 1.
The HOMO energies of substituted phenanthrotriphenylenes were found to be depending
on the electronic effects of methyl, fluoro functional groups and change in π–conjugation
on fusing extra benzenes with parent T1. For example, methylꢀsubstituted T2 and
fluorine substituted T10 (the derivative with two fluorine atoms) raised and lowered their
HOMO energy levels with respect to parent T1, respectively. The
phenanthrotriphenylenes T3 and T4 with multiple fluorine and chlorine atoms could not
oxidize as to give their HOMO energy levels in AC2 measurements. Interestingly, adding
four extra benzenes in T1 raised the HOMO energy of T13, in agreement with the notion
that electron removal could be easy from a more π–conjugated system. Also, based on
the similar fact, tetracene derivative had higherꢀlying HOMO level with respect to the
triphenylenes. The optical band gaps of T10, T12 and T14, which had more π–extended
polyfused frameworks, were lower compared to other derivatives.
Table 1. HOMO−LUMO energies of PAHs.
Compd.
aEHOMO
bELUMO
cEg
(eV)
(eV)
(eV)
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5.80
5.55
ꢀd
2.13
1.92
ꢀ
3.67
3.63
3.73
3.55
3.70
3.21
3.06
2.67
T1
T2
1
2
3
4
5
6
7
8
T3
ꢀd
ꢀ
T4
5.91
5.83
5.56
5.27
2.21
2.62
2.50
2.60
T9
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T10
T12
T14
aEHOMO was measured by photoelectron spectrometer (AC2). ELUMO = EHOMO − Eg.
cOptical band gap, Eg, was obtained from the absorption edge. dCompound samples were
not measurable in ACꢀ2 experiment.
b
Single crystal fieldꢀeffect transistor performance
To demonstrate the capability of these PAHs to be used as semiconductor, single crystals
of one of the derivatives, phenanthro[9,10:b]triphenylene (T1) were used as the channel
material in the fabrication of single crystal fieldꢀeffect transistor (SCFET) device.
Carefully chosen single crystals were placed on a glass substrate, with both ends painted
with colloidal graphite as the source and drain electrodes. After growing a thin layer of
parylene on top of the crystal as the dielectric, colloidal graphite was painted on top to
constitute a topꢀcontact, topꢀgate transistor device.19 The channel length, width and
parylene thickness were measured for each to be in the range of 1.0–0.5 mm, 0.25–0.20
mm, and 1.8–2.5 ꢁm, respectively (Figure S67, SI). Based on the data from 11 transistors,
an average hole mobility of 0.38 cm2Vꢀ1sꢀ1 was calculated and a maximum mobility of
1.15 cm2Vꢀ1sꢀ1 was observed, with an on/off ratio of ~104 (Table S2, SI).
Conclusions
In conclusion, we have successfully synthesized and characterized new series of PAHs
with extended conjugation from the phenanthrotriphenylene, tetracene and pentacene
backbones laterally or longitudinally. All new derivatives were characterized by NMR and
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highꢀresolution mass spectroscopy, while singleꢀcrystal X–ray analyses were also carried
out for selected derivatives. The planar PAHs derivatives adopt γ type packing motif,
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where the π faces stack parallel and shifted from each other. The nonꢀplanar PAHs show a
strong tendency to pack faceꢀtoꢀface for complementarity in shape. Those with multiple
chlorine atoms may also favor cofacial π–π stacking due to Cl⋅⋅⋅Cl interactions. One of the
derivatives, phenanthro[9,10:b]triphenylene was used to fabricate single crystal fieldꢀeffect
transistor and produced a maximum p–channel mobility of 1.15 cm2/Vꢀ1sꢀ1, with an onꢀoff
ratio of ~104.
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Experimental Section
The required starting materials were purchased from commercial sources and used without
further purification. Solvents were distilled and dried before performing
spectrophotometric, and spectrofluorimetric analyses. The coupling reactions such as
Suzuki coupling and Scholl reactions were carried out in nitrogen atmosphere. 1,4ꢀ
Dibromoꢀ2,5ꢀdiphenylbenzene (3)20 and 1,2ꢀdibromoꢀ4,5ꢀdiphenylbenzene (7)21 were
prepared according to known protocols. The purification of the compounds was carried out
by column chromatography using silica gel with 60ꢀ230 mesh size as the stationary phase.
Nuclear magnetic resonance spectra were recorded on a Bruker AMX400 O FTꢀNMR
spectrometer in chloroformꢀd1 with tetramethylsilane (TMS) as the internal standard. Vꢀ
550JASCOUV/VIS spectrophotometer was used to carry out absorption measurements
using dichloromethane as solvent. Single crystals were grown in a temperatureꢀgradient
copper tube by vapor phase transfer method with Argon as the carrier gas. The Xꢀray
diffraction was carried out on a Bruker X8APEX Xꢀray diffractometer with Mo Kα
radiation (λ = 0.71073 Å) and the structure was solved by SHELX 97 program. The
HOMO energies (EHOMO) of selected samples were measured by a photoelectron
spectrometer ACꢀ2 (Riken Keiki).
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Preparation of 1ꢀbromoꢀ2,4,5ꢀtriiodobenzene (9) 1ꢀbromoꢀ4ꢀiodobenzene (2.83 g, 10.0
mmol), iodine (3.56 g, 14.0 mmol) and KIO3 (1.50 g, 7.0 mmol) were dissolved in a
mixture of acetic acid (50 ml) and sulfuric acid (10 ml). The reaction mixture was heated
at 80 °C for 6 h. On completion of reaction, the mixture was cooled and poured into ice
water. The precipitated solid was filtered, washed with water and methanol to afford a
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white solid. Yield: 3.96 g, 74%. H NMR (CDCl3, 400 MHz) δ 8.27 (s, 1H), 8.05 (s, 1H).
13C NMR could not be recorded due to poor solubility of this derivative. HRMS (MALDIꢀ
TOF) m/z: [M]+ calcd for C6H2BrI3 533.6474; found 533.6464.
General procedure of Suzuki coupling on bromo/iodo benzenes The Suzuki coupling
reactions of bromo/iodo benzenes were performed with different mole ratio of aryl boronic
acids and Pd(PPh3)2Cl2 and PPh3. In fourꢀfold Suzuki coupling reactions of 1,2,4,5ꢀ
tetrabromobenzene (1), the compound (5.0 mmol) was mixed with aryl boronic acid (21.0
mmol), Pd(PPh3)2Cl2 (144 mg), PPh3 (104 mg) in a mixture of toluene (60 ml) and water
(20 ml). In twoꢀfold Suzuki coupling reactions of 1,4ꢀdibromoꢀ2,5ꢀdiiodobenzene (2), 1,4ꢀ
dibromoꢀ2,5ꢀdiarylbenzene (3–5), 1,2ꢀdibromoꢀ4,5ꢀdiiodobenzene (6), 1,2ꢀdibromoꢀ4,5ꢀ
diarylbenzene (7–8), these derivatives (5.0 mmol) were mixed with aryl boronic acid (11.0
mmol), Pd(PPh3)2Cl2 (72 mg), PPh3 (52 mg) in a mixture of toluene (60 ml) and water (20
ml). In threeꢀfold Suzuki coupling reactions of 1ꢀbromoꢀ2,4,5ꢀtriiodobenzene (9), the
compound (5.0 mmol) was mixed with aryl boronic acid (16.0 mmol), Pd(PPh3)2Cl2 (108
mg), PPh3 (78 mg) in toluene (60 ml) and water (20 ml) mixture. In oneꢀfold Suzuki
coupling reactions of 1ꢀbromoꢀ2,4,5ꢀtriarylbenzene (10–11), the compound (5.0 mmol)
was mixed with aryl boronic acid (6.0 mmol), Pd(PPh3)2Cl2 (36 mg), PPh3 (26 mg) in
toluene (60 ml) and water (20 ml) mixture.
The reaction mixture was heated to reflux for 24 h in nitrogen atmosphere. On completion
of the reaction, the product solution was cooled and the toluene layer was separated.
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Toluene was removed by rotary evaporator. The product was purified by column
chromatography using dichloromethane–hexane as the eluent to give a white powder.
Preparation of 1,4ꢀdibromoꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (4) Following the
general procedure, 1,4ꢀdibromoꢀ2,5ꢀdiiodobenzene (2) (2.44 g, 5.0 mmol) and
naphthaleneꢀ2ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to give the product as white
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powder. Yield: 1.71 g, 70%. H NMR (CDCl3, 400 MHz) δ 7.96ꢀ7.92 (m, 8H), 7.80 (s,
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2H), 7.64ꢀ7.61 (m, 2H), 7.58ꢀ7.54 (m, 4H). C NMR (CDCl3, 100 MHz) δ 143.0, 137.0,
135.5, 133.1, 132.9, 128.4, 128.3, 127.8, 127.7, 127.2, 126.6, 121.6. HRMS (MALDIꢀ
TOF) m/z: [M]+ calcd for C26H16Br2 485.9619; found 485.9637.
Preparation of 1,2ꢀdibromoꢀ4,5ꢀbis(naphthaleneꢀ1ꢀyl)benzene (5) Following the
general procedure, 1,4ꢀdibromoꢀ2,5ꢀdiiodobenzene (2) (2.44 g, 5.0 mmol) and
naphthaleneꢀ1ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to give the product as
1
powder. Yield: 1.66 g, 68%. H NMR (CDCl3, 400 MHz) δ 7.99ꢀ7.95 (m, 4H), 7.77 (s,
2H), 7.68ꢀ7.47 (m, 10H).13C NMR (CDCl3, 100 MHz) δ 142.3, 137.6, 135.5, 133.5, 131.4,
129.0, 128.8, 128.8, 128.2, 127.2, 126.5, 126.2, 125.8, 125.2, 123.1. HRMS (MALDIꢀ
TOF) m/z: [M]+ calcd for C26H16Br2 485.9619; found 485.9620.
Preparation of 1,2ꢀdibromoꢀ4,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (8) Following the
general reaction procedure, 1,2ꢀdibromoꢀ4,5ꢀdiiodobenzene (6) (2.44 g, 5.0 mmol) and
naphthaleneꢀ2ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to give the product as white
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powder. Yield: 1.81 g, 74%. H NMR (CDCl3, 400 MHz) δ 7.83 (s, 2H), 7.78ꢀ7.72 (m,
6H), 7.54 (d, J = 8.8 Hz 2H), 7.46ꢀ7.44 (m, 4H), 7.08ꢀ7.05 (m, 2H). 13C NMR (CDCl3, 100
MHz) δ 141.2, 136.8, 135.7, 133.3, 132.4, 128.4, 128.1, 127.6, 126.3, 123.9. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C26H16Br2 485.9619; found 485.9623.
Preparation of 1ꢀbromoꢀ2,4,5ꢀtriphenylbenzene (10) Following the general procedure,
1ꢀbromoꢀ2,4,5ꢀdiiodobenzene (9) (2.67 g, 5.0 mmol) and phenylboronic acid (1.95 g, 16.0
1
mmol) were reacted to give the product as white powder. Yield: 1.25 g, 65%. H NMR
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(CDCl3, 400 MHz) δ7.77 (s, 1H), 7.54ꢀ7.40 (m, 6H), 7.26ꢀ7.15 (m, 10H). 13C NMR
(CDCl3, 100 MHz) δ 141.5, 141.1, 140.6, 140.2, 139.9, 139.8, 134.9, 133.3, 129.7, 129.4,
128.2, 128.1, 128.0, 127.7, 127.0, 126.9, 121.4. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for
C24H17Br 384.0514; found 384.0523.
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Preparation of 1ꢀbromoꢀ2,4,5ꢀtris(naphthaleneꢀ2ꢀyl)benzene (11) Following the
general reaction procedure, 1ꢀbromoꢀ2,4,5ꢀdiiodobenzene (9) (2.67 g, 5.0 mmol) and
naphthaleneꢀ2ꢀboronic acid (2.75 g, 16.0mmol) were reacted to give the product as white
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powder. Yield: 1.85 g, 69%. H NMR (CDCl3, 400 MHz) δ 8.01 (s, 1H), 7.96ꢀ7.89 (m,
5H), 7.85 (s, 1H), 7.80ꢀ7.70 (m, 5H), 7.66 (s, 1H), 7.59ꢀ7.52 (m, 4H), 7.48ꢀ7.42 (m, 4H),
7.19ꢀ7.15 (m, 2H). 13C NMR (CDCl3, 100 MHz) δ 141.8, 141.2, 139.9, 138.1, 137.9,
137.5, 135.4, 134.1, 133.4, 133.2, 132.8, 132.4, 132.3, 128.5, 128.4, 128.3, 127.8, 127.6,
126.4, 126.2, 126.1, 121.9. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C36H23Br 534.0983;
found 534.0975.
General procedure for the preparation of 1,2,4,5ꢀtetraphenylbenzene (P1) Following
general reaction procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and
phenylboronic acid (2.56 g, 21.0 mmol) were reacted to give product as white powder.
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Yield: 1.76 g, 92%. H NMR (CDCl3, 400 MHz) δ 7.54 (s, 2H), 7.25ꢀ7.23 (m, 20H). C
NMR (CDCl3, 100 MHz) δ 141.0, 139.4, 139.6, 133.0, 129.9, 128.0, 126.6. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C30H22 382.1722; found 382.1726.
Preparation of 1,2,4,5ꢀtetrakis(4ꢀmethylphenyl)benzene (P2) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and paraꢀtolylboronic acid
(2.86 g, 21.0 mmol) were reacted to give the product as white powder. Yield: 1.93 g, 88%.
1H NMR (CDCl3, 400 MHz) δ 7.48 (s, 2H), 7.12 (t, J = 6.0 Hz, 8H), 7.06 (d, J = 8.0 Hz,
8H), 2.34 (s, 12H). 13C NMR (CDCl3, 100 MHz) δ 139.3, 138.2, 136.1, 133.0, 129.7,
128.7, 21.1.HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C34H30 438.2348; found 438.2359.
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Preparation of 1,2,4,5ꢀtetrakis(4ꢀfluorophenyl)benzene (P3) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 4-fluorophenylboronic
acid (2.94 g, 21.0 mmol) were reacted to give the product as white powder. Yield: 1.95 g,
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86%. H NMR (CDCl3, 400 MHz) δ 7.44 (s, 2H), 7.19ꢀ7.14 (m, 8H), 6.99ꢀ6.93 (m, 8H).
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13C NMR (CDCl3, 100 MHz) δ 163.2, 160.7, 138.8, 136.5, 132.8, 131.4, 131.3, 115.2,
115.0. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C30H18F4 454.1345; found 454.1348.
Preparation of 1,2,4,5ꢀtetrakis(4ꢀchlorophenyl)benzene (P4) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 4-chlorophenylboronic
acid (3.28 g, 21.0 mmol) were reacted to give the product as white powder. Yield: 2.08 g,
80%. 1H NMR (CDCl3, 400 MHz) δ 7.44 (s, 2H), 7.24 (d, J = 8.4 Hz, 8H), 7.12 (d, J = 8.4
Hz, 8H). 13C NMR (CDCl3, 100 MHz) δ 138.8, 138.7, 133.2, 132.7, 131.0, 128.5. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C30H18Cl4 518.0163; found 518.0154.
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Preparation of 1,2,4,5ꢀtetrakis(4ꢀmethoxyphenyl)benzene (P5) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 4-methoxyphenylboronic
acid (3.19 g, 21.0 mmol) were reacted to give the product as white powder. Yield: 2.06 g,
82%. 1H NMR (CDCl3, 400 MHz) δ 7.44 (s, 2H), 7.15 (t, J = 6.8 Hz, 8H), 6.80 (d, J = 8.4
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Hz, 8H), 3.80 (s, 12H). C NMR (CDCl3, 100 MHz) δ 158.3, 138.8, 133.6, 132.8, 129.0,
128.2, 113.4, 55.1.HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C34H30O4 502.2144; found
502.2148.
Preparation of 1,2,4,5ꢀtetra(naphthalenꢀ2ꢀyl)benzene (P6) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 2ꢀnaphthaleneboronic
acid (3.61 g, 21.0 mmol) were reacted to give the product as white powder. Yield: 2.04 g,
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70%. H NMR (CDCl3, 400 MHz) δ 7.97 (s, 4H), 7.94 (s, 2H), 7.91ꢀ7.72 (m, 8H), 7.65ꢀ
7.59 (m, 4H), 7.57ꢀ7.27 (m, 12H).13C NMR (CDCl3, 100 MHz) δ 138.4, 133.8, 132.7,
128.5, 128.2, 127.7, 126.3, 126.1, 126.0, 125.7. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for
C46H30 582.2348; found 582.2344.
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Preparation of 1,2,4,5ꢀtetra(naphthalenꢀ1ꢀyl)benzene (P7) Following the general
reaction procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 1ꢀ
naphthaleneboronic acid (3.61 g, 21.0 mmol) were reacted to give the product as white
powder. Yield: 2.21 g, 76%. Compound was partially soluble in most of the solvents and it
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could not be purified to get good Hand CNMR spectra. HRMS (MALDIꢀTOF) m/z:
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[M]+ calcd for C46H30 582.2348; found 582.2342.
Preparation of 1,2,4,5ꢀtetra(anthracenꢀ2ꢀyl)benzene (P8) Following the general
procedure, 1,2,4,5ꢀtetrabromobenzene (1) (1.97 g, 5.0 mmol) and 2ꢀanthraceneboronic
acid (4.66 g, 21.0 mmol) were reacted to give the product as white powder. The compound
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was almost insoluble in most of the solvents and it could not be purified to get good H
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and CNMR spectra. Yield: 3.13 g, 80%. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for
C62H38 782.2974; found 782.2984.
Preparation of 1,4ꢀdiphenylꢀ2,5ꢀbis(4ꢀfluorophenyl)benzene (P9) Following the general
procedure, 1,4ꢀdibromoꢀ2,5ꢀdiphenylbenzene (3) (1.94 g, 5.0 mmol) and 4ꢀ
fluorophenylboronic acid (1.54 g, 11.0 mmol) were reacted to give the product as white
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powder. Yield: 1.67 g, 80%. H NMR (CDCl3, 400 MHz) δ 7.49 (s, 2H), 7.29ꢀ7.16 (m,
14H), 6.97ꢀ6.92 (m, 4H). 13C NMR (CDCl3, 100 MHz) δ 163.1, 160.7, 140.7, 139.8,
138.7, 136.8, 132.8, 131.4, 129.8, 128.1, 126.8, 115.1, 114.8. HRMS (MALDIꢀTOF) m/z:
[M]+ calcd for C30H20F2 418.1533; found 418.1546.
Preparation of 1,4ꢀdiphenylꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P10) Following the
general procedure, 1,4ꢀdibromoꢀ2,5ꢀdiphenylbenzene (3) (1.94 g, 5.0 mmol) and
naphthaleneꢀ2ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to give product as white
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powder. Yield: 1.88 g, 78%. H NMR (CDCl3, 400 MHz) δ7.89 (s, 2H), 7.81ꢀ7.78 (m,
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4H), 7.71 (s, 2H), 7.48ꢀ7.46 (m, 4H), 7.32ꢀ7.30 (m, 4H), 7.26ꢀ7.22 (m, 8H), C NMR
(CDCl3, 100 MHz) δ 140.9, 139.9, 139.6, 138.7, 133.4, 132.2, 129.9, 128.5, 128.3, 128.1,
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128.0, 127.6, 127.2, 126.8, 126.0, 125.9. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for
C38H26 482.2035; found 482.2041.
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Preparation of 1,4ꢀbis(paraꢀtolyl)ꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P11) Following
general reaction procedure, 1,4ꢀdibromoꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (4) (2.44 g, 5.0
mmol) and paraꢀtolueneboronic acid (1.50 g, 11.0 mmol) were reacted to give product as
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white powder. Yield: 2.14 g, 84%. H NMR (CDCl3, 400 MHz) δ7.89 (s, 2H), 7.82ꢀ7.79
(m, 4H), 7.66 (d, J = 8.8 Hz 4H), 7.48ꢀ7.46 (m, 4H), 7.27ꢀ7.17 (m, 6H), 7.03 (d, J = 8.0 Hz
4H), 2.31 (s, 6H). 13C NMR (CDCl3, 100 MHz) δ 139.6, 139.5, 139.0, 137.9, 136.4, 133.5,
132.2, 129.8, 128.8, 128.4, 128.0, 127.6, 127.1, 125.9, 125.8, 21.1. HRMS (MALDIꢀTOF)
m/z: [M]+ calcd for C40H30 510.2348; found 510.2360.
Preparation of 1,4ꢀbis(naphthaleneꢀ1ꢀyl)ꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P12)
Following the general reaction procedure, 1,4ꢀdibromoꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene
(4) (2.44 g, 5.0 mmol) and naphthaleneꢀ1ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to
give the product as white powder. Yield: 2.39 g, 82%. 1H NMR (CDCl3, 400 MHz) δ 8.08ꢀ
8.01 (m, 2H), 7.87ꢀ7.78 (m, 8H), 7.66ꢀ7.59 (m, 4H), 7.47ꢀ7.34 (m, 12H), 7.19ꢀ7.16 (m,
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4H). C NMR could not be recorded due to poor solubility of this derivative. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C46H30 582.2348; found 582.2363.
Preparation of 1,4ꢀdiphenylꢀ2,5ꢀbis(anthraceneꢀ2ꢀyl)benzene (P13) Following the
general reaction procedure, 1,4ꢀdibromoꢀ2,5ꢀdiphenylbenzene (3) (1.94 g, 5.0 mmol)
andanthraceneꢀ2ꢀboronic acid (2.44 g, 11.0 mmol) were reacted to give product as white
powder. Yield: 2.33 g, 80%. The compound was partially soluble in most of the solvents
1
13
and was used directly for next reaction. H and C NMR could not be recorded due to
poor solubility of this derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C46H30
582.2348; found 582.2352.
Preparation of 1,2ꢀbis(naphthaleneꢀ1ꢀyl)ꢀ4,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P14)
Following the general reaction procedure, 1,2ꢀdibromoꢀ4,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene
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(8) (2.44 g, 5.0 mmol) and naphthaleneꢀ1ꢀboronic acid (1.89 g, 11.0 mmol) were reacted to
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2
3
1
give the product as white powder. Yield: 2.51 g, 86%. H NMR (CDCl3, 400 MHz) δ 8.10
4
5
(d, J = 8.0 Hz, 1H), 8.01ꢀ7.96 (m, 3H), 7.84ꢀ7.73 (m, 7H), 7.67ꢀ7.59 (m, 5H), 7.51ꢀ7.41
6
7
8
13
(m, 6H), 7.34ꢀ7.24 (m, 5H), 7.18ꢀ7.06 (m, 3H). C NMR could not be recorded due to
9
poor solubility of this derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C46H30
582.2348; found 582.2357.
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Preparation of 1ꢀ(4ꢀfluorophenyl)ꢀ2,4,5ꢀtriphenylbenzene (P15) Following the general
reaction procedure, 1ꢀdibromoꢀ2,4,5ꢀtriphenylbenzene (10) (1.93 g, 5.0 mmol) and 4ꢀ
fluorophenylboronic acid (0.84 g, 6.0 mmol) were reacted to give the product as white
1
powder. Yield: 1.66 g, 83%. H NMR (CDCl3, 400 MHz) δ 7.53 (s, 1H), 7.50 (s, 1H),
7.29ꢀ7.17 (m, 17H), 6.96ꢀ6.92 (m, 2H). 13C NMR (CDCl3, 100 MHz) δ 163.1, 160.6,
143.1, 140.9, 140.8, 139.8, 139.7, 138.6, 136.9, 133.0, 132.8, 131.4, 129.9, 128.1, 128.0,
126.7, 115.0, 114.8. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C30H21F 400.1627; found
400.1638.
Preparation of 1ꢀ(phenyl)ꢀ2,4,5ꢀtris(naphthaleneꢀ2ꢀyl)benzene (P16) Following the
general reaction procedure, 1ꢀdibromoꢀ2,4,5ꢀtris(naphthaleneꢀ2ꢀyl)benzene (11) (2.68 g,
5.0 mmol) and phenylboronic acid (0.73 g, 6.0 mmol) were reacted to give the product as
1
white powder. Yield: 2.40 g, 90%. H NMR (CDCl3, 400 MHz) δ 7.94 (s, 2H), 7.90 (s,
1H), 7.81ꢀ7.74 (m, 8H), 7.66 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.8 Hz, 2H), 7.47ꢀ7.43 (m,
6H), 7.33ꢀ7.31 (m, 2H), 7.27ꢀ7.23 (m, 6H).13C NMR (CDCl3, 100 MHz) δ 140.9, 140.1,
139.8, 138.7, 133.9, 133.6, 133.5, 132.2, 130.0, 128.5, 128.4, 128.2, 128.1, 127.6, 127.4,
127.3, 126.8, 126.0, 125.9. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C42H28 532.2191;
found 532.2198.
General
procedure
for
preparation
of
extensive
π–conjugates
of
phenanthrotriphenylene, tetracene and pentacene hydrocarbons 1,2,4,5ꢀtetraaryl
benzene (P1–P16) (1.0 mmol) was dissolved in anhydrous dichloromethane (60 ml). Iron
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chloride (3.24 g, 20.0 mmol), as dissolved in nitromethane (10 ml), was added via syringe
to the polyaryl solution. In case of P14 and P16 (4.86 g, 30.0 mmol), P6 (6.48 g, 40.0
mmol) and P8 (9.72 g, 60.0 mmol) different mole ratio of iron chloride was used.
The reaction mixture was stirred for 4–36 h at room temperature in nitrogen atmosphere.
On completion of reaction, the product was precipitated by adding methanol. The
precipitated product was washed with methanol and acetone, successively. The product
exhibited white to red color, depending on the conjugation in polyaromatic hydrocarbon.
Preparation of phenanthro[9,10:b]triphenylene (T1) Following the general procedure,
1,2,4,5ꢀtetraphenylbenzene (P1) (0.38 g, 1.0 mmol) and iron chloride were reacted for 18 h
to give the product as white solid. Yield: 0.31 g, 82%. The product was further purified by
vacuum sublimation in a temperature gradient oven at 440 °C/390 °C/350 °C (4.1*10−5
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1
Torr) to give 0.24 g (Yield: 78%). Mp: >300 °C. H NMR (CDCl3, 400 MHz) δ 9.94 (s,
2H), 8.98 (d, J = 8.0 Hz, 4H), 8.71 (d, J = 7.6 Hz, 4H), 7.80ꢀ7.71 (m, 8H).13C NMR could
not be recorded due to poor solubility of the derivative. HRMS (MALDIꢀTOF) m/z: [M]+
calcd for C30H18 378.1403; found 378.1407.
Preparation of 3,6,12,15ꢀtetramethylphenanthro[9,10:b]triphenylene (T2) Following
the general procedure, 1,2,4,5ꢀtetrakis(4ꢀmethylphenyl)benzene (P2) (0.44 g, 1.0 mmol)
and iron chloride were reacted for 12 h to give the product as white solid. Yield: 0.37 g,
86%. The product was further purified by vacuum sublimation in a temperature gradient
oven at 450 °C/400 °C/350 °C (4.3*10−5 Torr) to give 0.27 g (Yield: 72%). Mp: >300 °C.
1H NMR (CDCl3, 400 MHz) δ 9.77 (s, 2H), 8.81 (d, J = 8.4 Hz, 4H), 8.46 (s, 4H), 7.55 (d,
J = 8.0 Hz, 4H), 2.66 (s, 12H). 13C NMR could not be recorded due to poor solubility of
the derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C34H26 434.2029; found
434.2027.
Preparation of 3,6,12,15ꢀtetrafluorophenanthro[9,10:b]triphenylene (T3) Following
the general reaction procedure, 1,2,4,5ꢀtetrakis(4ꢀfluorophenyl)benzene (P3) (0.45 g, 1.0
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mmol) and iron chloride were reacted for 24 h to give the product as white solid. Yield:
0.35 g, 78%. The product was further purified by vacuum sublimation in a temperature
gradient oven at 480 °C/430 °C/380 °C (4.2*10−5 Torr) to give 0.25 g (Yield: 70%). Mp:
>300 °C. 1H NMR (C2D2Cl4, 400 MHz) δ 9.69 (s, 2H), 8.93ꢀ8.90 (m, 4H), 8.19 (d, J =
10.4 Hz, 4H), 7.57ꢀ7.52 (m, 4H). 13C NMR could not be recorded due to poor solubility of
the derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C30H14F4 450.1026; found
450.1015.
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Preparation of 3,6,12,15ꢀtetrachlorophenanthro[9,10:b]triphenylene (T4) Following
the general procedure, 1,2,4,5ꢀtetrakis(4ꢀchlorophenyl)benzene (P4) (0.52 g, 1.0 mmol)
and iron chloride were reacted for 48 h to give the product as white solid. Yield: 0.40 g,
77%. The product was further purified by vacuum sublimation in a temperature gradient
oven at 480 °C/430 °C/380 °C (6.3*10−5 Torr) to give 0.27 g (Yield: 68%). Mp: >300 °C.
1H NMR (C2D2Cl4, 400 MHz) δ 9.69 (s, 2H), 8.82 (d, J = 8.8 Hz, 4H), 8.55 (s, 4H), 7.76
(d, J = 7.6 Hz, 4H). 13C NMR could not be recorded due to poor solubility of the
derivative. HRMS (EI) m/z: [M]+ calcd for C30H14Cl4 513.9850; found 513.9855.
Preparation of 3,6,12,15ꢀtetramethoxyphenanthro[9,10:b]triphenylene (T5) Following
the general procedure, 1,2,4,5ꢀtetrakis(4ꢀmethoxyphenyl)benzene (P5) (0.50 g, 1.0 mmol)
and iron chloride were reacted for 4 h to give the product as white solid. Yield: 0.46 g,
93%. The product was further purified by vacuum sublimation in a temperature gradient
oven at 420 °C/380 °C/330 °C (9.6*10−5 Torr) to give 0.28 g (Yield: 60%). Mp: >300 °C.
1H NMR (CDCl3, 400 MHz) δ 9.57 (s, 2H), 8.80 (d, J = 8.8 Hz, 4H), 7.98 (s, 4H), 7.34 (d,
13
J = 8.0 Hz, 4H), 4.07 (s, 12H). C NMR could not be recorded due to poor solubility of
the derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C34H26O4 498.1826; found
498.1832.
Preparation
of
tetranaphtho[8,1,2ꢀcde:2',1',8'ꢀjkl:8'',1'',2''ꢀnop:2''',1''',8'''ꢀ
uva]pentacene (T6) Following the general procedure, 1,2,4,5ꢀtetra(naphthalenꢀ2ꢀ
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yl)benzene (P6) (0.58 g, 1.0 mmol) and iron chloride were reacted for 12 h to give the
product as red solid. Yield: 0.47 g, 81%. The product was further purified by vacuum
sublimation in a temperature gradient oven at 560 °C/510 °C/460 °C (6.4*10−5 Torr) to
give 0.20 g (Yield: 47%). Mp: >300 °C. 1H NMR and 13C NMR could not be recorded due
to poor solubility of the derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C46H22
574.1716; found 574.1708. The crystal structure was solved by Xꢀray diffraction.
Preparation of 5ꢀchloro tetrabenzo phenanthrotriphenylene (T7) Following the
general procedure, 1,2,4,5ꢀtetra(naphthalenꢀ1ꢀyl)benzene (P7) (0.58 g, 1.0 mmol) and iron
chloride were reacted for 12 h to give the product as yellow solid. Yield: 0.52 g, 72%. The
product was further purified by vacuum sublimation in a temperature gradient oven at 520
°C/470 °C/420 °C (8.1*10−5 Torr) to give 0.23 g (Yield: 44%). Mp: >300 °C. 1H NMR and
13C NMR could not be recorded due to poor solubility of the derivative. HRMS (MALDIꢀ
TOF) m/z: [M]+ calcd for C46H22Cl4 714.0476; found 714.0467.
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Attempted preparation of tetraanthraceno hexacene (T8) Following the general
procedure, 1,2,4,5ꢀtetra(anthracenꢀ2ꢀyl)benzene (P8) (0.78 g, 1.0 mmol) and iron chloride
were reacted for 36 h to give partially annulated products. This reaction did not lead to the
formation of completely annulated T9. MALDIꢀTOF mass of mixture containing partially
annulated derivatives was recorded.
Preparation of 3,12ꢀdifluorophenanthro[9,10:b]triphenylene (T9) Following the
general procedure, 1,4ꢀdiphenylꢀ2,5ꢀbis(4ꢀfluorophenyl)benzene (P9) (0.42 g, 1.0 mmol)
and iron chloride were reacted for 36 h to give the product as yellowꢀwhite solid. Yield:
0.34 g, 82%. The product was further purified by vacuum sublimation in a temperature
gradient oven at 480 °C/430 °C/380 °C (9.3*10−5 Torr) to give 0.27 g (Yield: 80%). Mp:
1
>300 °C. H NMR (CDCl3, 400 MHz) δ 9.83 (s, 2H), 8.96ꢀ8.92 (m, 4H), 8.57 (d, J = 7.6
Hz, 2H), 8.32 (d, J = 11.6 Hz, 2H), 7.82ꢀ7.72 (m, 4H), 7.52ꢀ7.47 (m, 2H). 13C NMR could
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not be recorded due to poor solubility of the derivative. HRMS (MALDIꢀTOF) m/z: [M]+
calcd for C30H16F2 414.1215; found 414.1223.
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2
3
4
5
6
7
8
9
Preparation of dibenzo phenanthrotriphenylene (T10) Following the general
procedure, 1,4ꢀdiphenylꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P10) (0.48 g, 1.0 mmol) and
iron chloride were reacted for 12 h to give the product as whiteꢀyellow solid. Yield: 0.42 g,
84%. The product was further purified by vacuum sublimation in a temperature gradient
oven at 460 °C/410 °C/360 °C (7.4*10−5 Torr) to give 0.28 g (Yield: 66%). Mp: >300 °C.
1H NMR (CDCl3, 400 MHz) δ 9.96 (s, 2H), 9.06ꢀ8.93 (s, 8H), 8.15ꢀ8.07 (m, 4H), 7.83ꢀ
7.64 (m, 8H).13C NMR could not be recorded due to poor solubility of the derivative.
HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C38H22 478.1719; found 478.1719.
Preparation of 3ꢀmethylꢀdibenzophenanthrotriphenylene (T11) Following the general
procedure, 1,4ꢀbis(paraꢀtolyl)ꢀ2,5ꢀbis(naphthaleneꢀ2ꢀyl)benzene (P11) (0.51 g, 1.0 mmol)
and iron chloride were reacted for 6 h to give the product as whiteꢀyellow solid. Yield:
0.45 g, 88%. Mp: >300 °C. 1H NMR (CDCl3, 400 MHz) δ 9.80 (s, 2H), 8.97ꢀ8.86 (m, 6H),
8.69 (s, 2H), 8.07 (s, 4H), 7.64ꢀ7.59 (m, 6H), 2.64 (s, 6H). 13C NMR could not be recorded
due to poor solubility of the derivative. HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C40H26
506.2029; found 506.2034.
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11
12
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Preparation of tetrabenzophenanthrotriphenylene (T12) Following the general
procedure,1,4ꢀbis(naphthaleneꢀ2ꢀyl)ꢀ2,5ꢀbis(naphthaleneꢀ1ꢀyl)benzene (P12) (0.51 g, 1.0
mmol) and iron chloride were reacted for 8 h to give the product as yellow solid. Yield:
0.52 g, 90%. The product was further purified by vacuum sublimation in a temperature
gradient oven at 520 °C/480 °C/420 °C (6.4*10−5 Torr) to give 0.29 g (Yield: 56%). Mp:
>300 °C. 1H NMR (CDCl3, 400 MHz) δ10.33 (s, 2H), 9.45 (d, J = 7.6 Hz, 2H), 8.99ꢀ8.84
(s, 6H), 8.18ꢀ8.07 (m, 8H), 7.88 (t, J = 6.8 Hz, 2H), 7.77 (t, J = 7.2 Hz, 2H), 7.69ꢀ7.64 (m,
4H). 13C NMR could not be recorded due to poor solubility of the derivative. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C46H26 578.2029; found 578.2037.
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Preparation of 3ꢀchloroꢀdinaphthophenanthrotriphenylene (T13) Following the
general procedure, 1,4ꢀdiphenylꢀ2,5ꢀbis(anthracenꢀ2ꢀyl)benzene (P13) (0.51 g, 1.0 mmol)
and iron chloride were reacted for 24 h to give the product as yellow solid. Yield: 0.49 g,
76%. The product was further purified by vacuum sublimation in a temperature gradient
oven at 520 °C/470 °C/420 °C (6.3*10−5 Torr) to give 0.20 g (Yield: 40%). Mp: >300 °C.
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13
1H NMR and C NMR could not be recorded due to poor solubility of the derivative.
HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C46H24Cl2 646.1255; found 646.1262. The
crystal structure was solved by xꢀray diffraction.
Preparation of tetranaphtho tetracene (T14) Following the general procedure, 1,2ꢀ
bis(naphthaleneꢀ2ꢀyl)ꢀ4,5ꢀbis(naphthaleneꢀ1ꢀyl)benzene (P14) (0.51 g, 1.0 mmol) and iron
chloride were reacted for 8 h to give the product as orange color solid. Yield: 0.51 g, 88%.
The product was further purified by vacuum sublimation in a temperature gradient oven at
1
520 °C/480 °C/430 °C (6.3*10−5 Torr) to give 0.21 g (Yield: 42%). Mp: >300 °C. H
NMR (CDCl3, 400 MHz) δ 10.53 (s, 2H), 9.43 (d, J = 8.4 Hz, 2H), 9.01 (d, J = 8.8 Hz,
2H), 8.79 (d, J = 7.6 Hz, 2H), 8.70 (d, J = 8.8 Hz, 2H), 8.22ꢀ8.09 (m, 8H), 7.93ꢀ7.75 (m,
6H).13C NMR could not be recorded due to poor solubility of the derivative. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C46H24 576.1873; found 576.1879.
Preparation of 3ꢀfluorophenanthro[9,10:b]triphenylene (T15) Following the general
procedure, 1ꢀ(4ꢀfluorophenyl)ꢀ2,4,5ꢀtriphenylbenzene (P15) (0.40 g, 1.0 mmol) and iron
chloride were reacted for 24 h to give the product as white solid. Yield: 0.36 g, 86%. Mp:
>300 °C. 1H NMR (CDCl3, 400 MHz) δ 9.89 (s, 1H), 9.80 (s, 1H), 8.95ꢀ8.85 (m, 4H), 8.69
(d, J = 7.6 Hz, 2H), 8.55 (d, J = 8.8 Hz, 1H), 8.29 (d, J = 6.8 Hz, 1H), 7.81ꢀ7.71 (m, 6H),
7.59ꢀ7.50 (m, 1H).13C NMR could not be recorded due to poor solubility of the derivative.
HRMS (MALDIꢀTOF) m/z: [M]+ calcd for C30H17F 396.1314; found 396.1322.
Preparation of tetranaphthobenzotetracene (T16) Following the general procedure, 1ꢀ
(phenyl)ꢀ2,4,5ꢀtris(naphthaleneꢀ2ꢀyl)benzene (P16) (0.53 g, 1.0 mmol) and iron chloride
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were reacted for 12 h to give product as brown solid. Yield: 0.45 g, 86%. Mp: >300 °C. 1H
NMR (CDCl3, 400 MHz) δ 9.93 (s, 1H), 9.84 (s, 1H), 8.97 (d, J = 8.8 Hz, 1H), 8.93ꢀ8.85
(m, 4H), 8.79 (d, J = 8.8 Hz, 1H), 8.61 (d, J = 7.6 Hz, 2H), 8.08ꢀ7.98 (m, 6H),7.79ꢀ7.63
(m, 6H).13C NMR could not be recorded due to poor solubility of this derivative. HRMS
(MALDIꢀTOF) m/z: [M]+ calcd for C42H22 526.1722; found 526.1725.
ASSOCIATED CONTENT
Page 26 of 32
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Supporting Information
The Supporting information including Xꢀray crystallography data, additional mass spectra,
1H and 13C NMR spectra, absorption spectra, and photophysical data for complete
spectroscopic analysis is available free of charge on the ACS Publications website.
AUTHOR INFORMATION
Corresponding Author
*Prof. YuꢀTai Tao, Eꢀmail: ytt@gate.sinica.edu.tw Fax: +886ꢀ2ꢀ27831237 Tel: +886ꢀ2ꢀ
27898580.
ACKNOWLEDGMENT
Financial support from Ministry of Science and Technology, Taiwan (Grant Number: 103ꢀ
2120ꢀMꢀ009ꢀ003ꢀCC1) is gratefully acknowledged.
REFERENCES
1.
(a) Ball, M.; Zhong, Y.; Wu, Y.; Schenck, C.; Ng, F.; Steigerwald, M.; Xiao, S.;
Nuckolls, C. Contorted Polycyclic Aromatics. Acc. Chem. Res. 2015, 48, 267ꢀ276. (b)
Zhang, C.; Chen, P.; Hu, W. Organic FieldꢀEffect TransistorꢀBased Gas Sensors. Chem. Soc.
Rev. 2015, 44, 2087ꢀ2107. (c) Mei, J.; Diao, Y.; Appleton, A. L.; Fang, L.; Bao, Z.
Integrated Materials Design of Organic Semiconductors for FieldꢀEffect Transistors J. Am.
Chem. Soc. 2013, 135, 6724ꢀ6746. (d) Chase, D. T.; Fix, A. G.; Kang, S. J.; Rose, B. D.;
Weber, C. D.; Zhong, Y.; Zakharov, L. N.; Lonergan, M. C.; Nuckolls, C.; Haley, M. M.
6,12ꢀDiarylindeno[1,2ꢀb]fluorenes; Syntheses, Photophysics, and Ambipolar OFETs. J.
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Am. Chem. Soc. 2012, 134, 10349ꢀ10352. (e) Roberson, L. B.; Kowalik, J.; Tolbert, L. M.;
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