Persulfurated Coronene: A New Generation of “Sulflower”

Article abstract of DOI:10.1021/jacs.6b12630

We report the first synthesis of a persulfurated polycyclic aromatic hydrocarbon (PAH) as a next-generation “sulflower.” In this novel PAH, disulfide units establish an all-sulfur periphery around a coronene core. The structure, electronic properties, and redox behavior were investigated by microscopic, spectroscopic and electrochemical methods and supported by density functional theory. The sulfur-rich character of persulfurated coronene renders it a promising cathode material for lithium-sulfur batteries, displaying a high capacity of 520 mAh g^-1 after 120 cycles at 0.6 C with a high-capacity retention of 90%.

Full text of DOI:10.1021/jacs.6b12630

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Communication
Persulfurated Coronene: A New Generation of “Sulflower”
Renhao Dong, Martin Pfeffermann, Dmitry Skidin, Faxing Wang, Yubin Fu, Akimitsu Narita, Matteo
Tommasini, Francesca Moresco, Gianaurelio Cuniberti, Reinhard Berger, Klaus Müllen, and Xinliang Feng
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b12630 • Publication Date (Web): 27 Jan 2017
Downloaded from http://pubs.acs.org on January 27, 2017
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Persulfurated Coronene: A New Generation of “Sulflower”
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Renhao Dong, Martin Pfeffermann, Dmitry Skidin, Faxing Wang, Yubin Fu, Akimitsu Narita,
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Matteo Tommasini, Francesca Moresco, Gianaurelio Cuniberti, Reinhard Berger, Klaus Müllen,
Xinliang Feng*
,†
†
Department of Chemistry and Food Chemistry, Center for Advancing Electronics Dresden, Technische Universität Dresden,
01062 Dresden, Germany
§
Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
‡
Institute for Materials Science, Max Bergmann Center of Biomaterials, and Center for Advancing Electronics Dresden, TU
Dresden, 01069 Dresden, Germany
‖Dipartimento di Chimica, Materiali ed Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32,
20133 Milano, Italy
Supporting Information Placeholder
1,2,3,4,5,6,7,8,9,10,11,12-dodecachlorocoronene (2, C24Cl12) was
ABSTRACT: We report the first synthesis of a persulfurated pol-
9
prepared according to our previous report. Nucleophilic replace-
ment of all peripheral chloro substituents was achieved using lith-
ium benzylthiolate at room temperature, which afforded
ycyclic aromatic hydrocarbon (PAH) as a next-generation “sul-
flower.” In this novel PAH, disulfide units establish an all-sulfur
periphery around a coronene core. The structure, electronic proper-
ties, and redox behavior were investigated by microscopic, spectro-
scopic and electrochemical methods and supported by density func-
tional theory (DFT). The sulfur-rich character of persulfurated cor-
onene renders it a promising cathode material for lithium-sulfur
1
,2,3,4,5,6,7,8,9,10,11,12-dodecakis(benzylthio)coronene (3) as a
red powder in 62% yield. After reductive cleavage of the protective
benzyl groups under Birch conditions using lithium in anhydrous
liquid ammonia at -78 °C, the dodecalithio coronene-
1,2,3,4,5,6,7,8,9,10,11,12-dodecathiolate (4) was obtained. The
subsequent direct treatment of compound 4 with aqueous hydrogen
chloride and hydrogen peroxide afforded the desired product 5 in
-1
batteries, displaying a high capacity of 520 mAh g after 120 cy-
cles at 0.6 C with a high-capacity retention of 90%.
6
1% isolated yield over two steps as a dark-red solid after washing
in refluxing toluene.
Over the last few decades, great efforts have been dedicated to the
synthesis of sulfur-rich polycyclic aromatic hydrocarbons (PAHs)
such as acene sulfide, hexathiotriphenylene, hexathienocoro-
1
2
3
,
4
5
nene, sulfur-annelated hexa-peri-hexabenzocoronenes (HBCs),
6
and sym-tribenzotetrathienocoronenes. They exhibit unique redox
behavior and promising charge transport properties for organic
field effect transistors (OFETs) and organic photovoltaics (OPVs).
However, fully sulfur-substituted PAHs carrying fused disulfide
bonds at the periphery have not yet been achieved. Persulfur-sub-
stituted benzene (C S ) was reported by Sü1zle et al. in 1989 but
6 6
was only detected as charged fragment during the mass spectromet-
ric investigation of benzo[1,2-d: 3,4-d’: 5,6-d”]-tri(1,3-dithiol-2-
one) after the extrusion of three CO molecules (Figure 1 left). In
006, the appealing structure of octathio[8]circulene (C16S ), also
8
known as "sulflower" (Figure 1 middle), was reported by Nenaj-
denko et al. This molecule can be considered as the first generation
of "sulflowers", featuring a D8h-symmetrical structure with eight
sulfur atoms at the peripheral positions. However, this compound
contains one eight-membered central ring fused with eight thio-
phene units, which possess a rather small π-delocalized carbon
framework. Thereby, the full sulfuration of the periphery of large
PAH cores remains a challenge.
7
Figure 1. “Sulflower” molecules: (left) persulfurated benzene
); (middle) fully sulfur-substituted circulene (C16
persulfurated coronene (C24
2
(
C
6
S
6
8
S ); (right)
S
12).
8
The detailed synthetic procedure and characterization data of
intermediates are described in Supporting Information (section
1.2). Due to the low solubility of compound 5 in common organic
solvents, characterization by NMR spectroscopy or growth of sin-
gle crystals was not possible, even at elevated temperatures. Nev-
ertheless, matrix-assisted laser desorption/ionization time-of-flight
mass spectroscopy (MALDI-TOF MS) analysis displayed a clear
peak at m/z = 671.6629, consistent with the expected mass calcu-
Herein, we report the synthesis and characterization of an un-
precedented persulfurated coronene (5, C24S12) with an all-sulfur
terminated edge structure, which we consider as a next-generation
“sulflower” (Figure 1 right). The synthesis of compound 5 was car-
ried out as depicted in Scheme 1. Starting from coronene (1),
lated for C24
S12, i.e., 671.6648 (Figure 2a). The isotopic distribution
observed for the obtained PSC sample was in perfect agreement
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-
1
with the pattern simulated for chemical formula C24
ing the complete sulfuration (Figure 2a, inset).
S
12, corroborat-
intensity between 545 and 800 cm remain ambiguous for weak C-
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S absorptions, a more prominent absorption peak occurred at 971
cm for the C-S stretching vibration. The band at 509 cm is a typ-
ical IR absorption for S-S stretching. A weak band at 930 cm
939 cm in DFT-calculated spectrum) reflects the breathing mode
-
1
-1
Scheme 1. Synthetic Route Towards Persulfurated Coronene
11a
-1
a
(PSC, 5) and Perthiolated Coronene (PTC, 6)
-1
(
of the ring containing the stretching S-S bond.
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aReagents and conditions: (i) AlCl
(
Li, THF, methanol, NH , -78 °C to rt, 4 h; HCl/H O /water, rt, 61%;
3 2 2
, ICl, CCl
ii) benzyl mercaptan, NaH, DMI, 0 °C to rt, 16 h, 62%; (iii and iv)
3
4
, 81 °C, 48 h, 93%;
4
(v) NaBH .
Figure 3. Low-temperature STM characterization of single PSC 5
molecules on the Au (111) surface. (a) STM image showing two
PSC 5 molecules adsorbed on an Au (111) terrace at the kink sites
(
I = 20 pA, U = 0.7 V); (b) STM image of a PSC 5 molecule (I =20
pA, U = 0.5 V); (c) Line scan taken along the molecule in (b); (d)
dI/dV spectra of the molecule in (b): bare Au surface (blue curve),
center of the molecule (red curve), edge of the molecule (black
curve).
Scanning tunneling microscopy (STM) is a powerful tool for
the characterization of single molecules on metal surfaces, thus we
performed low-temperature STM studies to visualize compound
1
3
5
.
Upon adsorption by thermal sublimation, single molecules
were present either at the kink sites of the Au (111) herringbone
reconstruction (Figure 3a and Figure S2) or at the step edges. The
molecules showed a characteristic hexagonal shape, in accord with
the six-fold symmetry formed by the outer disulfide bridges (Figure
3b). According to the line scan in Figure 3c, the central core of the
molecule was imaged as a depression, and all sulfur atoms formed
a homogeneous ring around the core. The observed hexagonal spe-
cies can be unambiguously assigned to intact 5 (Figure 3 b and Fig-
ure S3). The possibility of the desulfuration of 5 during sublimation
can be excluded (for TGA curves see Figure S4) because full desul-
furation would produce pristine coronene, which is known to ap-
pear as a uniform, flower-shaped molecule rather than a centrosym-
Figure 2. Spectroscopic structure proof of persulfurated coronene
5, PSC). (a) HR-MALDI-TOF MS spectrum. Inset: isotopic distri-
bution compared with the mass spectrum simulated for C24
(
S
12. (b)
Raman spectrum (blue) compared with results from DFT calcula-
tions (red) over the D and G regions. Inset: the enlarged experi-
mental and calculated curves from 200 cm to 600 cm . (c and d)
IR spectrum (blue) compared with DFT calculation (red).
-
1
-1
13b
metric molecule on Au (111), whereas partial desulfuration
To further confirm the structure of 5, the compound was char-
acterized by Raman spectroscopy with an excitation wavelength of
would yield shapes of lower symmetry. Moreover, dI/dV spectros-
copy measurements were performed on 5 (Figure 3d). Although the
spectrum obtained over the central part (red curve) simply resem-
bles the spectrum of a bare gold surface (blue curve), there is a clear
resonance peak at 1.2 V in the spectrum obtained over an edge
5
32 nm (Figure 2b). The main expected features of graphene-like
molecules were observed for 5 (blue line in Figure 2b). A compar-
ison with CVD graphene can be found in Figure S1, namely D
-
1
-1
10
(1382 cm ) and G (1594 cm ) bands. In the low-wavenumber
region of the Raman spectrum, weak signals appeared at 256, 392
(black curve). The STM measurements thus confirm the full edge
-
1
sulfuration on coronene for compound 5.
and 482 cm , which are typically assigned to C-S bond in plane
Compound 5 can be reduced in solution to afford perthiolated
coronene (6) via the cleavage of S-S bonds. A suspension of the
compound 5 was treated with sodium borohydride in DMF under
argon protection to obtain 6 as a red powder after drying. The PTC
bending, C-S bond deformation and S-S bond from 5, respectively
1
1
(
inset in Figure 2b). Specific peak assignments are summarized
in Table S1 of the Supporting Information. The calculated Raman
spectrum is in agreement with the experimental results (red line in
Figure 2b). In addition, the IR spectrum of 5 was measured and
compared with a spectrum calculated by density functional theory
(DFT) (Figure 2c and d, Table S2). Although the signals of weak
6
exhibits much better solubility in some organic solvents (such as
DMF and DMSO) than PSC 5. Characterization by MALDI-TOF
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MS, H- and 13C-NMR, and element analysis unambiguously re-
vealed the structure of 6 (see Supporting Information 1.2). Typi-
cally, the MALDI-TOF MS analysis displayed an intense signal at
1
Coulombic efficiency (ICE) of 85%. Such performance is well
comparable with that of reported organic-based matrix/sulfur com-
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1,14,15
posites and S
8
-encapsulated cathodes.
During the first dis-
m/z = 685.1338, in agreement with its expected molecular mass cal-
charge cycle, the voltage plateau occurred at ~1.8 V, whereas the
voltage plateau increased and remained stable at ~2.0 V over the
subsequent cycles (Figure S7). This observation is distinct from
what has been typically observed in previously reported cases of
1
culated for C24
S
12
H12, i.e., 685.1321. The H-NMR spectrum
showed only one signal at δ = 4.11 ppm attributed to the -SH groups
of 6 in deuterated DMSO, which disappeared upon further addition
of D
2
O, indicating the successful formation of 6.
S
8
, in which a two-step discharge plateau is observed: the formation
of Li polysulfide species (Li , n≥4) at the first discharge plateau
of 2.35 V and the final product of Li
2 n
S
1
4
2
S at ~2.1 V. As a result, a
one-electron transfer process was proposed to describe the lithia-
tion mechanism along with the formation of LiS complexes and the
reforming of disulfides (Figure S8). Moreover, compound 5 exhib-
ited stable cycling performance (Figure 5b). After 120 cycles, a ca-
pacity of 520 mAh/g was retained and 90% Coulombic efficiency
was recorded at 0.6 C, revealing the excellent electrochemical per-
formances using the sulfurated PAHs as cathode materials in lith-
ium-sulfur batteries.
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Figure 4. (a) UV/Vis absorption spectrum of PSC 5 (blue) and PTC
-6
6
(pink) in NMP (5 × 10 M). (b) Cyclic voltammogram of 5 in
THF solution of Bu NPF (0.1 M) with a scan rate of 50 mV/s. (c)
4
6
Electrostatic potential of 5. (d) Molecular orbitals of 5 by DFT cal-
culation (B3LYP/6-31G (d, p)). Left: LUMO; right: HOMO, the
orbital energies are given in eV.
Despite the low solubility of 5, its UV/Vis absorption spectrum
could be measured in N-methyl-2-pyrrolidone (NMP) (Figure 4a),
which displayed a weak and broad absorption between 400 and 600
nm. The optical energy gap of 5 was determined to be 2.1 eV from
the onset of its UV/Vis absorption spectrum (Table S3). In contrast,
after reduction by NaBH , compound 6 showed three pronounced
4
absorption peaks at 314, 380, and 508 nm. The successive reduction
could be monitored by studying the UV/Vis absorption spectra as a
function of the amount of NaBH
4
(Figure S5) and reaction time
(Figure S6). The electrochemical properties of 5 were investigated
by cyclic voltammetry (CV) in THF solution (Figure 4b). The en-
ergy of the highest occupied molecular orbital (HOMO) was esti-
mated from the onset of the first oxidation peak to be -4.23 eV for
Figure 5. Electrochemical performance of PSC 5 molecules as
cathode materials of lithium-sulfur batteries. (a) First discharge
(red) and charge (blue) curves of PSC measured at 0.6 C in the po-
5
(Table S3). The lowest unoccupied molecular orbital (LUMO)
+
energy level was calculated based on the corresponding HOMO
level and optical energy gap, as listed in Table S3.
To further investigate the effect of persulfuration on the mo-
lecular orbital of the PAHs, DFT calculations were performed at
the B3LYP/6-31G (d, p) level (more calculations are shown in SI
tential range of 1-3 V vs. Li/Li . (b) Capacity (blue) and Coulombic
efficiencies (red) versus cycle number for PSC molecules. The blue
circles report capacities relative to the weight of the active sulfur
species in the cathode.
In summary, we demonstrated a novel synthetic protocol for
producing the first fully sulfur-substituted PAH as a new generation
of carbon-sulfur “sulflower” bearing a coronene core. Microscopy
and spectroscopy analyses provided explicit proof of the formation
of compound 5 with a fully disulfide-bond-edged (S-S) structure.
Its sulfur-rich character renders 5 a promising cathode material for
lithium-sulfur battery system. The protocol established in this work
offers unique access to larger PAHs and graphene (or graphene na-
noribbons) with persulfurated edges and paves the way toward
promising applications in OFETs, OPVs, energy, and superconduc-
tor-related areas.
6
). Figure 4c shows the electrostatic potential of 5 on the 0.002 iso-
density surface. Here, the periphery of 5 displays electron-donating
properties, particularly at the S-S bonds. In addition, the shapes of
the HOMO and the LUMO are presented in Figure 4d. Interest-
ingly, the LUMO is not delocalized over the carbon framework but
exclusively localized on and in between the sulfur atoms. The
HOMO and LUMO energy levels of 5 are -5.31 and -3.27 eV, re-
spectively, yielding a HOMO-LUMO gap of 2.04 eV (Table S3),
which is consistent with the optical results.
Its sulfur-rich feature and redox behavior render compound 5 a
promising active cathode material for lithium-sulfur batteries. In
addition, the low solubility of 5 in most organic solvents makes it
possible to perform continuous charge/discharge cycles. Figure 5a
displays the first discharge-charge voltage profiles of 5 attained at
0.6 C (1 C = 1675 mA/g). The initial discharge/charge capacities
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
s s
were 424 mAh/g and 496 mAh/g , leading to an exceptional initial
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Experimental details, NMR, MALDI-TOF MS, UV/Vis absorption
spectra, STM
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AUTHOR INFORMATION
Corresponding Author
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(6) Zhang, Q.; Peng, H.; Zhang, G.; Lu, Q.; Chang, J.; Dong, Y.; Shi, X.;
*
*
muellen@mpip-mainz.mpg.de
xinliang.feng@tu-dresden.de
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Notes
The authors declare no competing financial interests.
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ACKNOWLEDGMENT
This work was financially supported by the ERC Grant on
(11) (a) Wei, S.; Ma, L.; Hendrickson, K. E.; Tu, Z.; Archer, L. A. J. Am.
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DMATER and EC under Graphene Flagship (No. CNECT-ICT-
04391). The German Excellence Initiative via the Cluster of Ex-
Chem. Soc. 2015, 137, 12143. (b) Talapaneni, S. N.; Hwang, T. H.; Je, S.
H.; Buyukcakir, O.; Choi, J. W.; Coskun, A. Angew. Chem., Int. Ed. 2016,
cellence EXC1056 “Center for Advancing Electronics Dresden”
cfaed) and the International Helmholtz Research School Nanonet
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28, 3158.
(
(12) Zmolek, P. B.; Sohn, H.; Gantzel, P. K.; Trogler, W. C. J. Am. Chem.
are gratefully acknowledged. R.H.D. appreciates funding from the
Alexander von Humboldt-Foundation. We thank Dr. Yuanzhi Tan,
Dr. Ajayakumar Murugan Rathamony, Dr. Junzhi Liu, Dr. Xiao-
dong Zhuang, Mr. Justus Krüger, and Mr. Frank Eisenhut for the
helpful discussion.
Soc. 2001, 123, 1199.
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