Vibrational Properties and Polymerization of Corannulene under

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C: Physical Processes in Nanomaterials and Nanostructures

Vibrational Properties and Polymerization of Corannulene under Pressure Probed by Raman and Infrared Spectroscopy Mingrun Du, Jiajun Dong, Ying Zhang, Xigui Yang, Zepeng Li, Mingchao Wang, Ran Liu, Bo Liu, Qingjun Zhou, Tong Wei, and Bingbing Liu J. Phys. Chem. C, Just Accepted Manuscript • Publication Date (Web): 03 Sep 2019 Downloaded from pubs.acs.org on September 3, 2019

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The Journal of Physical Chemistry

Vibrational Properties and Polymerization of Corannulene under Pressure Probed by Raman and Infrared Spectroscopy Mingrun Du1, 2*, Jiajun Dong2, Ying Zhang2, Xigui Yang3, Zepeng Li1*, Mingchao Wang1, Ran Liu2, Bo Liu2, Qingjun Zhou1, Tong Wei1, Bingbing Liu2

1

College of Science, Civil Aviation University of China, Tianjin 300300, China.

2

State Key Laboratory of Superhard Materials, College of Physics, Jilin University,

Changchun 130012, China. 3

School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001, China.

*Corresponding Authors E-mail: [email protected], [email protected]

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Abstract Here, we report a high-pressure study on corannulene up to 27.6 GPa using the diamond cell technique assisted with Raman and infrared spectroscopic measurements. The intermolecular interactions between corannulene are modulated upon compression, inducing two transitions at 2.2 and 3.6 GPa. Above 11.4 GPa, the bowl-shaped corannulene is highly compressed and deformed and irreversibly polymerized due to crosslinking of the aromatic systems under pressure. Above 19.7 GPa, the sample is further polymerized and transformed into an amorphous sp2/sp3 mixed hydrocarbon phase. A comparison with planar coronene suggests that the molecular curvature may have little influence on the transformations of 2D polycyclic aromatic hydrocarbons (PAHs) in the low-pressure range. Relative to closed-cage C60, the open-cell corannulene is more unstable upon compression. Our results reveal the structural transformation of corannulene under pressure and present an important example for the high-pressure study of bowl-shaped PAHs.


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Introduction Polycyclic aromatic hydrocarbons (PAHs) are built from assemblies of polygonal faces of carbon. Because of their exceptional chemical and physical properties, PAHs exhibit great potential in many advanced applications, such as superconductors, organic electronic and optical devices.1-5 It is well known that the structure and properties of PAH-based materials can be efficiently modified by applying external pressures.6-17 Davydov et al. demonstrated that some PAHs, such as naphthalene, anthracene, pentacene, perylene and coronene, could transform into graphite or diamond under high-pressure

and

high-temperature

conditions.6

For

K-doped

picene,

the

superconductive critical temperature (Tc) of its 18-K phase increases linearly with pressure up to 1.2 GPa, while that of its 7-K phase exhibits a negative pressure dependence.7 Furthermore, pentacene exhibits metallic character with a positive temperature coefficient of resistance at 27 GPa.8 Therefore, investigating the structures and properties of different types of PAHs under pressure is always of great importance for extending their applications and designing novel carbon-based materials. As an important member of PAHs, corannulene (C20H10) has a bowl-shaped sp2hybridized carbon framework composed of a cyclopentane ring fused with 5 benzene rings; this structure distinguishes corannulene from more traditional flat-plane PAHs and provides several intriguing properties, such as a significant dipole moment, bowlto-bowl inversion and potential fluorescent and electronic properties. The unique curved structure of corannulene can be seen as the smallest curved subunit of C60 and a part of the end cap of carbon nanotubes. Due to this structural resemblance, corannulene is generally regarded as a primary model for experimental and theoretical investigations of nonplanar π-surfaces.18-23 It has been reported that bowl-shaped PAHs, such as sumanene and corannulene, show different packing structures depending on the molecular curvature, size and symmetry, while planar π-conjugated PAH molecules, such as coronene, prefer to form a stacking structure due to the effective π-π interactions.24, 25 Thus, new structure and property transitional mechanisms of PAHs under pressure may be observed from compressing bowl-shaped PAHs. However, in contrast to broadly studied flat-plane PAHs,10-13 few high-pressure data of bowl-shaped



PAHs, especially corannulene, are available.26 From this perspective, it is valuable to study the pressure behaviors of corannulene, which can provide an important example for the high-pressure study of the bowl-shaped PAH family. According to the recent Raman study of corannulene,26 at least two transitions are observed in the pressure range from 0.53 to 8 GPa, while the underlying mechanisms of these transitions are still unclear. Moreover, the knowledge of vibrational and structural properties of corannulene above 10 GPa are still lacking. In this work, we report the vibrational properties and polymerization of corannulene under pressure using Raman and infrared (IR) spectroscopy. The highest experimental pressure is 27.6 GPa. Our principal aim is to investigate the pressure behaviors of both internal and external vibrational modes of corannulene to explore the structural deformation, phase transitions and chemical stability of corannulene at high pressures. Such knowledge should contribute to the development of new strategies for the creation of new carbon structures with desirable properties based on bowl-shaped PAH materials.

Experimental Methods Corannulene (97% purity) was purchased from J & K Chemical Ltd. and used without further purification and recrystallization. High-pressure experiments were performed in a Mao-Bell type diamond anvil cell (DAC) at room temperature. The corannulene was loaded into a steel gasket, which was preindented to a thickness of 40 μm, and a 100 μm hole acted as the sample chamber. Two type-Ia diamonds with 0.3 mm culets were installed in the DAC for in situ Raman measurements, while two typeIIa diamonds with 0.2 mm culets were used as anvils for in situ IR measurements. No pressure transmitting medium (PTM) was used for the Raman measurements, while KBr was used as the PTM for IR measurements. A small ruby ball (~10 um) was incorporated with the sample for pressure calibration by measurements of the fluorescence line shift. The highest pressure for in situ Raman and IR measurements was 27.6 GPa. A Renishaw 1000 notch filter spectrometer (Renishaw inVia) equipped with a


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Raman microscope (OLYMPUS, objective: 50x/0.35) and two wavelength (785 nm and 532 nm) lasers were used for the high-pressure Raman measurements, giving a resolution of 1 cm−1. Upon compression, there is a massive increase in the luminescence background signal of the Raman spectra using near-infrared (785 nm) excitation. In comparison to using a 785 nm laser for the Raman analysis, the use of a 532 nm laser as the excitation source led to a considerable reduction in the pressureinduced luminescence background from the compressed corannulene above 11.4 GPa. The laser powers at the sample were less than 5 mW for the two excitation sources. IR measurements were carried out using a Bruker Vertex80 V FTIR spectrometer. Resolution and number of coadded scans were 4 cm-1 and 256, respectively. The Raman and IR peaks were analyzed with Lorentzian functions.

Results and discussion It is well known that Raman and IR spectroscopic methods are powerful tools for characterizing PAH molecules under high pressure and can detect chemical bonding and local structural transformation of the compressed sample.9-13, 16, 17, 26 According to group theory analysis, corannulene possesses 720 fundamental modes (180 Ag + 180 Bg + 180 Au + 180 Bu), where one Au mode and two Bu modes are acoustic modes. As the structure of corannulene is centrosymmetric, a phonon mode is either Raman (Ag and Bg) or IR (Au and Bu) active. No silent mode is expected.27-29 It is reported that among the 360 Raman active modes of corannulene expected from the theory, approximately 40 lines can be identified in the experimental spectra.27 Figure 1 shows the Raman spectra of corannulene measured using a 785 nm laser at ambient and high pressures. The ambient Raman spectra of corannulene shown in the bottom of Figure 1a and b are in good agreement with those reported in previous literatures,27, 29 in which the observed Raman modes can be divided into three general categories: (1) the intermolecular Raman modes observed below 110 cm-1, which correspond to mixed libration and rotation or librations where molecules collectively move out of their plane; (2) the intramolecular Raman modes assigned to out-of-plane atomic displacements located between 167 and 663 cm-1; and (3) the intramolecular



Raman modes assigned to atomic displacements in the corannulene plane observed in the frequency range of 850 - 1613 cm-1.27 Table 1 lists the most intense peaks in the spectra and the assignments of their vibration types within the corannulene molecules.27, 29

From the recorded spectra up to 16.3 GPa, we note that the Raman peaks of corannulene shift, weaken, broaden and split with increasing pressure. At 1.7 - 2.2 GPa, the intramolecular Raman modes initially located at 165, 549, 595 and 1430 cm-1 split, leading to the appearances of new peaks around 191, 555, 595, 609 and 1438 cm-1. These results are consistent with the previously reported appearances of new corannulene Raman modes around 550, 600, and 1435 cm-1 at 2.79 GPa .26 Above 9.4 GPa, most of the corannulene Raman peaks assigned to intermolecular and out-of-plane atomic displacement vibrations merge with the background. However, the broad Raman peaks assigned to atomic displacements in the corannulene plane can still be traced in the high-frequency range (1000 to 1800 cm-1). These results suggest that the bowlshaped molecular structure of corannulene is highly compressed and deformed above 9.4 GPa; thus, the out-of-plane inter- and intramolecular vibrations are unfavorable due to increasing electrostatic repulsion of the atoms by the molecules above and below each corannulene molecule. A similar effect of pressure on the out-of-plane intramolecular vibration modes is also observed in the high-pressure Raman data of coronene.10 Because of the increasing luminescent background under pressure, we have difficulty resolving the broad Raman peaks in the spectra above 9.4 GPa. The occurrence of the luminescent background signal may result from the shortened distance between molecules at high pressures, where one may observe orbital overlap between two adjacent π-conjugated molecules (creating a new molecular orbital across two molecules),30 or from excited structural defects similar to pyrene.31

We further plot the wavenumbers of the corannulene Raman modes as functions of pressures in Figure 2a, b and c, and the numerical values of the slopes for Raman shift versus pressure are shown in Table 2. Upon compression to 2.2 GPa, the pressure dependences of the selected intermolecular Raman modes exhibit obvious changes in slopes due to the decreased intermolecular space under pressure, which alters the van


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der Waals forces between molecules.(Figure 2a) The pressure slopes of 69, 75, 85, 101 cm-1 modes decrease from initial 15.95, 15.19, 20.65, 23.93 cm-1/GPa to 9.31, 10.72, 17.65,18.57 cm-1/GPa, respectively.(Table 2) Such slope changes together with the splitting of the intramolecular Raman peaks initially located at 165, 549, 595 and 1430 cm-1 provide evidences of phase transition at the pressure range of 1.7 to 2.2 GPa. At around 3.6 GPa, the pressure slopes of intermolecular and out-of-plane intramolecular Raman modes significantly decrease (Figure 2a and b, Table 2), while no distinct changes are observed in the pressure dependences of the in-plane intramolecular Raman modes at such pressure. (Figure 2c) This difference is attributed to the intermolecular distortions being greater than those in-plane intramolecular under applied pressure or the deviatoric stress induced by the compression without using PTM.32, 33 With a further increase in pressure to 9.4 GPa, there is a change in the slope value of the plot for the 1430 cm-1 peak, and the remaining Raman modes in the figure disappear. As discussed above, this is likely due to the significant deformation of the bowl-shape structure of corannulene molecule at such high pressure. These anomalies observed in the Raman spectra thus indicate three phase transitions in the sample at 2.2, 3.6 and 9.4 GPa. In addition, Alvarez et al. reported similar pressure slope changes of corannulene intermolecular modes at around 2.79 (the slopes of peaks at 40-90 (108) cm-1 are around 9.8 (23.2) cm-1/GPa at 0.5 - 2.06 GPa and decrease to around 7.7 (14.05) cm-1/GPa at 2.79 - 4 GPa) and 4 GPa, and the disappearances of most Raman modes at 9 GPa, which further support our assignment of the transitions at 2.2, 3.6 and 9.4 GPa.26 Notably, in contrast to our work, Alvarez and his colleagues compressed corannulene using 4 : 1 methanol–ethanol as the PTM, which is used for providing hydrostatic pressure conditions in the DAC to 10 GPa.26, 34 Therefore, in our work the observed transitions below 9.4 GPa should be related to the pressure-enhanced interactions and distortions of corannulene molecules rather than the deviatoric stress in the sample chamber. To detect possible phase transitions at higher pressure, we further perform Raman measurements on the sample by using a 532 nm laser in the pressure range from 11 to 26 GPa, and the spectra are shown in Figure 3. It should be noted that by using a 532 nm laser, the luminescence background is strong enough to obscure most Raman



spectral features of corannulene in the pressure range of 2.7 - 9.5 GPa. (Figure S1) However, as the pressure increases above 11.4 GPa, the luminescence background signal redshifts enough to pass the frequency range (100 to 1800 cm-1) where our Raman measurements are performed. Thus, Raman spectra of corannulene could be clearly obtained above this pressure. Above 11.4 GPa, most Raman peaks of corannulene disappear, and only two broad peaks in the high-frequency range, corresponding to the in-plane atomic displacement modes initially located at 1423 1613 cm-1, can be observed. This is in agreement with the Raman spectra shown in Figure 1. Upon compression to 19.8 GPa, only a single asymmetrical broad peak located at 1400 to 1800 cm-1 can be observed, indicating the transformation of corannulene into an amorphous material similar to the amorphous hydrogenated carbon structure obtained in the pressure-induced reaction of benzene and other polycyclic aromatic hydrocarbons.9, 11, 35, 36 Furthermore, the color of the sample in the cell changes to deep red at ~11.4 GPa and turns black above 17.9 GPa, which also suggests the appearance of phase transitions in the sample at these two pressure points. (Figure S2) On the other hand, the remarkable color change of the sample upon compression is a direct result of pressure closing the HOMO-LUMO gap of the corannulene molecule and the increasing size of corannulene polymers.9, 37-39 High-pressure IR spectra of corannulene are collected at room temperature up to 27.6 GPa, and some selected spectra are shown in Figure 4a. The ambient spectrum of the sample is consistent with those reported in other theoretical and experimental studies.27, 29 The assignments of several strong IR peaks are also shown in Table 1. From the figure, we can observe that the IR peaks of the sample become weaker and broader as the pressure increases. The 548 and 661 cm-1 peaks (the out-of-plane external carbon bending modes) and 838 cm-1 peak (out-of-plane ring bending combined CH wagging mode) split at 3.6 - 5 GPa. Above 11.5 GPa, the out-of-plane external carbon bending modes at 520 - 720 cm-1 become weak, broad and featureless, and the CH stretching modes at 3000 - 3500 cm-1 combine into one broad peak. These results indicate the significant deformation of the bowl-shaped structure of corannulene above 11.5 GPa. Strikingly, a broad peak at 2937 cm-1 increases in intensity when the pressure


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overpasses 11.5 GPa, and it ultimately dominates the spectrum range from 2700 to 3500 cm-1 up to the highest pressure. Such IR peak can be assigned to the CH stretching mode involving sp3 carbon atoms,9, 16, 40 implying the polymerization between corannulene molecules in the sample. Upon compression to 19.7 GPa, almost all the IR peaks at 520 - 1800 cm-1 become too weak to be observed, suggesting the significant amorphization of the sample. In contrast, the new strong CH stretching mode at around 3000 cm-1 can still be clearly identified. To precisely determine the pressures at which the possible phase transitions occur, the pressure dependences of the IR modes are plotted in Figure 4b. It is clear that the 548, 661 and 838 cm-1 peaks split at 3.6 ~ 5 GPa, and there are obvious discontinuities in the data for all the intramolecular IR modes at 11.5 GPa. Above 19.7 GPa, all the selected IR modes disappear in the spectrum. These results are consistent with our highpressure Raman results, suggesting phase transitions of the sample at 3.6, 11.5 and 19.7 GPa. To investigate the reversibility of the phase transitions in corannulene under pressure, we measure the Raman and IR spectra of samples quenched from 14.3 and 27 GPa, which are presented in Figure 5a and b, respectively. Figure 5c shows the corresponding images of these two decompressed samples, which are taken with an optical microscope. The sample quenched from 14.3 GPa is transparent and exhibits a strong luminescent background, which makes all Raman features of this sample obscured and not visible (Figure S3). The IR modes of the corannulene molecule recover after decompression, while the modes become weak and broad compared with those of the pristine sample, and a new broad band corresponding to the CH stretching mode involving sp3 carbon is observed at around 2923 cm-1.9, 16, 40 These results indicate that part of the corannulene has irreversibly polymerized at 14.3 GPa. After the decompression from 27 GPa, the sample is opaque, and only two broad Raman bands at 1438 and 1554 cm-1 are preserved in its Raman spectrum, indicating the irreversible amorphization of corannulene molecules. The 1438 cm-1 band likely evolved from the Ag mode of corannulene initially located at 1431 cm-1; the 1554 cm-1 band likely corresponds to C-C/C=C bonds and is generally observed in the Raman spectra of



amorphous fullerenes or fullerene fragments containing hexagonal and pentagonal carbon rings.41-44 Compared with the sample quenched from 14.3 GPa, the intensity of the new CH stretching IR mode at 2923 cm-1 is dramatically enhanced when decompressed from 27 GPa. This finding implies that the amount of polymerized corannulene in the sample increases upon further compression, thus improving the sp3 content of the sample. Furthermore, most IR peaks related to the carbon skeleton vibrations of corannulene become very weak or disappear in IR spectrum of the sample quenched from 27 GPa, while the strong and broad CH vibrational peaks at 827 (arising from the Oop ring bending + CH wagging mode of corannulene), 2923 (sp3 CH stretching) and 3023 (sp2 CH stretching) cm-1 can be clearly traced in the spectrum. 9, 16, 27, 29, 40

These results provide evidence for the formation of mixed sp2 and sp3 amorphous

hydrogenated carbon phases in the decompressed sample. The possible reaction mechanisms for the polymerization and amorphization of corannulene under pressure are the crosslinking of the aromatic ring systems via cycloaddition reactions. In this case, pressure induces the mixing of orbitals, resulting in dearomatization via a ringopening mechanism, and thus, the aromatic corannulene molecules polymerize via the aromatic site.9, 36, 45 The bowl-shaped corannulene molecule can be regarded as the building block of a C60 molecule with its pentagonal ring surrounded by hexagons, which are often discussed in comparison with flat-plane coronene and with C60 molecules. In this view, it is worth comparing the structural transitions and properties of corannulene under pressure to those of coronene and C60 crystals, which may provide new insight into the high-pressure behaviors of PAHs. Our high-pressure Raman and IR results of corannulene reveal two phase transitions at 2.2 and 3.6 GPa. Similar phase transitions are observed in coronene at 1.3 and 3.7 GPa, where the different phases are due to changes in intermolecular interactions and intramolecular distortions.10 This similarity is likely due to the two-dimensional (2D) structures of corannulene and coronene, suggesting that the curvature of PAHs may have little influence on their structural transitions in the low-pressure range. At 14.3 GPa, part of the corannulene have irreversibly polymerized and their bowl-shaped structures are highly deformed. Upon


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further compression, the corannulene starts to transform into an amorphous carbon phase above 19.7 GPa and irreversibly amorphizes at 27 GPa. In contrast, the deformed C60 molecules in compressed C60 crystals are almost reversible even after decompressing from ~ 30 GPa.44, 46 These results suggest that the open-cell molecule, corannulene, is more unstable compared to the closed C60 molecule under pressure.

Conclusions In summary, we have studied the Raman and IR spectra of corannulene under pressures up to 27.6 GPa. The obvious changes in the peak position and spectroscopic features identified four phase transitions during the compression. Upon compression, the pressure-enhanced intermolecular interactions and molecule distortion induce two transitions at 2.2 and 3.6 GPa. Above 11.4 GPa, the corannulene molecules are highly deformed and start to irreversibly polymerize. Above 19.7 GPa, the corannulene transforms into mixed sp2 and sp3 amorphous hydrocarbon phases. The polymerization and amorphization of corannulene probably proceed through crosslinking of the aromatic ring systems via cycloaddition reactions. A comparison with coronene suggests that the curvature of 2D PAHs has little influence on their structural transitions in the low-pressure range. Furthermore, corannulene is more unstable than C60, probably due to its open-cell structure. The compression behaviors of corannulene reported here reveal the structural transformations and polymerization of this molecule under pressure. Such knowledge would help in the design of new carbon structure with desirable properties based on PAH materials.

Acknowledgements The authors gratefully acknowledge funding support from the National Natural Science Foundation of China (11804384, 11804307, 51802343, 51772326), Scientific Research Foundation of Civil Aviation University of China (2017QD23X), National Key R & D Program of China (No. 2018YFA0305900), Scientific Research Project of



Tianjin Education Committee (2018KJ254), the Fundamental Research Funds for the Central Universities (3122018L006), and Open Project of State Key Laboratory of Superhard Materials (Jilin University) (201803).

Supporting Information Available: Raman spectra up to 9.5 GPa obtained with a 532 nm laser. (Figure S1) Images of corannulene in the sample cell at selected pressures. (Figure S2) The Raman spectrum of the sample quenched from 14.3 GPa using a 532nm laser (Figure S3) This material is available free of charge via the Internet at http://pubs.acs.org.

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Table 1. Assignments and frequencies (cm-1) of several vibrational modes of corannulene in comparison with references at ambient conditions.28, 30 Raman mode (cm-1)

IR mode (cm-1)

Referencea

This work

Assignmenta

Referencea

This work

Assignmenta

65

69

Intermolecular mode

546

548

Bu Oop external carbon bending

75

76

Intermolecular mode

659

661

Au Oop external carbon bending

82

85

Intermolecular mode

838

838

Bu Oop ring bending + CH wagging

108

101

Intermolecular mode

1133

1134

Bu in plane δ(CH)

167

165

Bg Oop rim carbon wagging

1311

1314

Au in plane [δ(hexa) + δ(penta)]

172-182

182

Ag oop molecule bending

1435

1434

Bu in plane [ν(CrimCext) + δ(CH)]

549

549

Ag oop external carbon bending

595

595

Ag oop external carbon bending

1432

1431

Ag in plane [ν(CrimCrim) + δ(penta)] + δ(CH)]

1453

1452

Bg in plane [ν(CrimCrim) + δ(penta)]

1613a

1626

in plane [ν(CrimCrim) +

1625b

1632

δ(CextCpenta) + ν(CextCpenta)] in plane ν(CextCpenta)

a. ref 27, b. ref 29; Oop, hexa, penta, ext abbreviations are respectively used for out of plane, hexagone, pentagone and external. δ is used for bending and ν for stretching.



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Table 2. Observed pressure dependences of the Raman shifts at room temperature. The pressure dependences of the Raman shift were obtained from least-squares fits of the experimental data to a linear equation. Raman Modes of

Pressure dependences of Raman shift in different pressure range (cm-1/GPa)

corannulene

0 ~ 1.7 GPa

2.2 ~ 3.1 GPa

3.6 ~ 8.4 GPa

69

15.95

9.31

4.18

76

15.19

10.72

5.14

85

20.65

17.65

7.31

101

23.93

18.57

7.73

165

9.56

11.18

7.76

14.15

8.11

9.4 ~ 11.2 GPa

(cm-1)

182

18.23

549

2.91

595

1430

4.67

2.41

8.64 3.13

1.32

3.86

1.80

3.38

1.80

3.87

2.37

5.09

2.60

2.72 3.21


-0.10

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Figure Captions:

Figure 1. Representative Raman spectra of corannulene in the frequency ranges of 50750 cm-1 (a) and 800-1800 cm-1 (b) below 8.4 GPa. Selected Raman spectra of corannulene collected in the pressure range of 9.4-16.3 GPa. (c) The excitation wavelength is 785 nm.

Figure 2. Pressure dependences of intermolecular Raman modes (a), out-of-plane intramolecular Raman modes (b) and in-plane intramolecular Raman modes (c) observed in corannulene at room temperature. The shadow areas indicate the possible phase boundaries.

Figure 3. Selected Raman spectra of corannulene collected in the pressure range of 11. 4 - 25.7 GPa. The excitation wavelength is 532 nm.

Figure 4. (a) The IR spectra of corannulene up to 27.6 GPa. (b) The pressure dependences of several IR modes.

Figure 5. (a) The Raman spectrum of corannulene decompressed from 27 GPa using 532 nm excitation. (b) IR spectra of pristine sample and samples decompressed from 14.3 and 27 GPa. The asterisks indicate the appearances of the new IR peaks located at 2923 cm-1 in the spectra. (c) The optical images of samples decompressed from 14.3 and 27 GPa under back illumination.



Figure 1

Figure 1. Representative Raman spectra of corannulene in the frequency ranges of 50750 cm-1 (a) and 800-1800 cm-1 (b) below 8.4 GPa. Selected Raman spectra of corannulene collected in the pressure range of 9.4-16.3 GPa. (c) The excitation wavelength is 785 nm.


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Figure 2

Figure 2. Pressure dependences of intermolecular Raman modes (a), out-of-plane intramolecular Raman modes (b) and in-plane intramolecular Raman modes (c) observed in corannulene at room temperature. The shadow areas indicate the possible phase boundaries.



Figure 3



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Figure 4




Figure 5

Figure 5. (a) The Raman spectrum of corannulene decompressed from 27 GPa using 532 nm excitation. (b) IR spectra of pristine sample and samples decompressed from 14.3 and 27 GPa. The asterisks indicate the appearances of the new IR peaks located at 2923 cm-1 in the spectra. (c) The optical images of samples decompressed from 14.3 and 27 GPa under back illumination.


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TOC Graphic



Figure 1. Representative Raman spectra of corannulene in the frequency ranges of 50-750 cm-1 (a) and 800-1800 cm-1 (b) below 8.4 GPa. Selected Raman spectra of corannulene collected in the pressure range of 9.4-16.3 GPa. (c) The excitation wavelength is 785 nm.


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Figure 2. Pressure dependences of intermolecular Raman modes (a), out-of-plane intramolecular Raman modes (b) and in-plane intramolecular Raman modes (c) observed in corannulene at room temperature. The shadow areas indicate the possible phase boundaries. 160x118mm (300 x 300 DPI)





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Figure 5. (a) The Raman spectrum of corannulene decompressed from 27 GPa using 532 nm excitation. (b) IR spectra of pristine sample and samples decompressed from 14.3 and 27 GPa. The asterisks indicate the appearances of the new IR peaks located at 2923 cm-1 in the spectra. (c) The optical images of samples decompressed from 14.3 and 27 GPa under back illumination. 182x62mm (300 x 300 DPI)


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TOC graphic 84x47mm (300 x 300 DPI)


Vibrational Properties and Polymerization of Corannulene under

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