Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing

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C: Plasmonics; Optical, Magnetic, and Hybrid Materials

Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing –CONHC H Chains at 500 K 14

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Jianyun Wu, Takashi Takeda, Norihisa Hoshino, Yasutaka Suzuki, Jun Kawamata, and Tomoyuki Akutagawa J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b03866 • Publication Date (Web): 21 Aug 2019 Downloaded from pubs.acs.org on August 22, 2019

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The Journal of Physical Chemistry

Ferroelectricity of a Tetraphenylporphyrin Derivative Bearing –CONHC14H29 Chains at 500 K Jianyun Wu,† Takashi Takeda,†, ‡ Norihisa Hoshino,†, ‡ Yasutaka Suzuki, Jun Kawamata, and Tomoyuki Akutagawa †, ‡*

†Graduate

School of Engineering, Tohoku University, Sendai 980-8579, Japan,

Graduate School of

Medicine, Yamaguchi University, Yamaguchi, Yamaguchi 753-8512, Japan, and ‡Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to)

Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 21-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

Phone:

+81-22-217-5653 ACS Paragon Plus Environment

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The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Fax:

+81-22-217-5655

E-mail

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Abstract: Optical properties of porphyrin derivatives were used to fabricate an artificial light-harvesting system. The introduction of a N-H•••O= hydrogen-bonding alkylamide chain (-CONHCnH2n+1) into a functional

-system is among the useful approaches to design multifunctional supramolecular

assemblies. The tetraphenylporphyrin derivative bearing four –CONHC14H29 chains (1) shows the successive and reversible phase transition behavior of S1-S2 at 338 K, S2-Colr at 444 K, and Colr-I (isotropic liquid) at 564 K, where a fluidic discotic rectangular columnar (Colr) liquid crystal phase was observed in a wide temperature range of 444–564 K before melting. The one-dimensional columnar molecular assembly of (1)C was constructed using a simultaneous operation of N-H•••O= hydrogenbonding and -stacking interactions. Temperature (T)- and frequency (f)-dependent dielectric constants of 1 indicated characteristic dielectric enhancement at higher-T and lower-f conditions above 500 K because of the thermally activated motional freedom of the polar N-H•••O= hydrogen-bonding unit in the Colr phase. The polarization–electric field (P-E) curves at f = 0.1 Hz clearly indicated ferroelectric hysteresis behavior with a remanent polarization (Pr) of 1 Ccm-2 and a coercive electric field (Ec) of 2 V m-1 at 503 K. The stable operation of the high-T ferroelectrics at approximately 500 K facilitates the potential application of a memory device in a high-T environment.


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1. Introduction

Various molecular structures in an aromatic

-electronic system have been utilized for designing

systems with -functionalities such as electrical conductivity, magnetic behavior, and optical properties. For example, pentacene and pyrene derivatives have shown excellent electrical conducting and emission behaviors, respectively.1-5 To further the molecular design, introduction of hetero-atoms such as B, N, P, and S into the C-based -conjugated molecular structure has been extensively examined to enhance the variation in the electronic structure of the present -molecular system.6-18 Highly polarized S-atoms within the -electron-donating molecular framework enable an increase in the intermolecular interaction, transfer integrals, and carrier transport property,12-14 whereas the simultaneous introduction of both B and N atoms into the

system forms a boron-dipyrromethane

-framework and B-N containing

aromatic hydrocarbons with high emission and quantum yield of ~100%.15-18 In simple terms, the introduction of one N atom into benzene (C6H6) generates a pyridine (C5NH5) framework, imparting a basic property because of the proton-accepting N site. In contrast, biologically important lightharvesting -systems such as porphyrin and cyanine dyes show several N-atoms within a

-planar

molecular framework.19-23 Most of these systems belong to the metal-coordinated macrocycles containing basic N-sites simultaneously bearing high redox activity and light absorption ability. Among them, a complex molecular assembly structure of the light-harvesting Mg-coordinated porphyrin derivative exist as chlorophylls of protein; the chemical design and assembly control of the porphyrins are among the interesting research targets for fabricating an artificial energy conversion system.24,

25

Various molecular assembly structures of porphyrin derivatives have been designed as cyclic, onedimensional (1D), and two-dimensional (2D) array structures for specific optical responses.26-30 1D stacking columnar structures have been designed through the introduction of hydrogen-bonding and/or hydrophobic interactions, resulting in a discotic columnar liquid crystal phase and/or organogels.31, 32


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Hydrogen-bonding functional -molecules bearing alkylamide (-CONHCnH2n+1) chains were examined for the formation of 1D molecular assembly structures.33-45 Simple benzene derivatives bearing multiple –CONHCnH2n+1 chains form a stable thermotropic discotic hexagonal columnar (Colh) liquid crystal phase, whose thermal phase transition behavior is governed by the intermolecular N-H•••O= hydrogenbonding interaction.33 The application of an outer electric field along the N-H•••O= hydrogen-bonding 1D column induces a collective dipole inversion along the direction of the 1D hydrogen-bonding chain, indicating a ferroelectric polarization-electric field (P-E) hysteresis during the Colh phase.39-45 From a systematic evaluation of various alkylamide-substituted benzene derivatives, three types of molecules, 1,4- (2BC), 1,3,5- (3BC), and 1,2,3,4,5- (5BC) alkylamide-substituted benzene derivatives, indicated ferroelectric P-E hysteresis during the Colh phase.45 However, intrinsic

-functionalities such as

electrical conductivity and emission are difficult to design in a simple benzene derivative. Therefore, we designed a highly emissive pyrene derivative (4PC) bearing four –CONHC14H29 chains that showed a blue-green fluorescence conversion because of monomer-excimer formation, fluorescent organogels, nanofibers, and a Colh liquid crystal phase as well as ferroelectricity and current-switching behavior according to the ferroelectric local electric field.46 Recently, we also designed an extended -system of hexaphenyltriphenylene and non- -planar helicene derivatives bearing multiple –CONHC14H29 chains to design new organic ferroelectrics.47,

48

The latter racemic helicene derivative bearing two –

CONHC14H29 chains showed an excellent ferroelectric parameter of Pr = 11.1 C cm-2 and Ec = 20 V m-1, because of the formation of a 2D lamellar (La) liquid crystalline phase with a considerably high density of hydrogen-bonding sites.48 The chemical design of the central

core is among the essential

factors to show the liquid crystalline property, ferroelectricity, and multifunctionality of the supramolecular assemblies. In addition, there are several approaches for designing new types of organic ferroelectrics based on intermolecular proton-transfer,49-51 atomic displacement,52, rotators.54-57

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and molecular

The one-dimensional columnar polar molecular assemblies have been designed by the

hydrogen-bonding interactions of N-H•••O= amide type in plastic crystalline state dipeptide column with a ferroelectric Pr = 0.44

58

and homomeric

C cm-2.59 Interestingly, one-dimensional polar


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columnar assemblies of the non-planar bowl-shaped corannulene derivative and fan-shaped supramolecular assembly indicated both the ferroelectricity and SHG activity in the columnar mesophase phases, where the application of the electric filed inverted the direction of dipole moment.6064

Soft molecular assemblies becomes one of the potential candidates for the dynamic polar inversion

environment.

Herein, we focused on the -planar tetraphenylporphrin derivative (1) bearing four –CONHC14H29 chains, whose molecular assembly structure and ferroelectric response were discussed. Although the preparation of molecule 1 has already been reported by Shi et al.,67 the application of a photovoltaic cell was attempted by Liu et al.68 However, both the dielectric and/or ferroelectric responses of the NH•••O= hydrogen-bonding molecular assembly of 1 have unfortunately not yet been examined. The dynamic behavior of the N-H•••O= amide-type hydrogen-bonding interaction enables the design of new ferroelectrics based on an optically interesting porphyrin

core. The infinite 1D N-H•••O= hydrogen-

bonding chain along the -stacking column can realize a collective dipole inversion along the hydrogenbonding direction, inverting the macroscale polarization via the application of an outer electric field along the -stacking direction (Scheme 1). Herein, the hydrogen-bonding molecule assembly of 1 was examined in terms of phase transition behavior, dielectric response, and ferroelectricity.

CONHC14H29

C14H29HNOC

N

O

N H

R N H

N

N H N

O R N H O

C14H29HNOC

1

CONHC14H29

R N H O R N H

N H H N

N

H N R O H N R O H N R O H N R O

Scheme 1. Molecular structure of the hydrogen-bonding tetraphenylporphrin derivative 1 and a schematic representation of the 1D ferroelectric columnar supramolecular assembly. The


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application of an electric field along the

-stacking column generates a collective dipole

inversion of the 1D N-H•••O= hydrogen-bonding direction and macroscale polarization.

2. Experimental Section

Commercially available chemical reagents and solvents were employed for the preparation of 1 and were used without further purification. Molecule 1 was prepared from the corresponding tetraphenylporphirin tetracarboxylic acid according to literature procedures.67-69

1H

NMR

spectra were recorded on a Bruker Advance III 400 NMR spectrometer, and chemical shifts ( ) were expressed in ppm relative to tetramethylsilane (1H, 0.00 ppm) as an internal standard. The measurement of temperature-dependent infrared (IR, 400-4000 cm; ) spectra was carried out on KBr pellets using a Thermo Fisher Scientific Nicolet 6700 spectrophotometer with a resolution of 4 cm; .

Morphology of molecular assemblies 1 on HOPG substrate was

observed by a SEM using a JEOL JSPM-5200, which were fabricated by the cast method on HOPG substrate using CHCl3 solution (1x10-4 M). TG-DTA analyses were carried out using a Rigaku Thermo plus TG8120 thermal analysis station using an Al2O3 reference in the temperature range from 300 to 780 K with a heating rate of 5 K min-1 under nitrogen and the


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DSC analyses were carried out using a METTLER thermal analysis DSC1-TS station using an Al2O3 reference in the temperature range from 173 to 550 K with the heating and cooling rate of 5 K min-1 under N2 condition. Temperature dependent powder X-ray diffraction (PXRD) patterns were collected using a Rigaku Rint-Ultima III diffractometer with a Cu-K radiation at A = 0.154187 nm. The P-E curve was measured by the commercially available ferroelectric tester (Precision LC, Radiant Technologies). The liquid crystalline state of 1 was fabricated into the ITO glass (SZ-A311P6N), which was sandwiched by the corresponding ITO glass to form the dielectric measurement cell with an average electrode gap of 2 m. Intermolecular NH•••O= hydrogen-bonding

-dimer structure of -CONHCH3 substituted tetraphenylporphyrin

derivative was optimized by DFT calculation with a B3LYP/6-31g (d, p) basis-set,70 in order to simplify the calculations.

The intensity of the SHG activity was measured using the Kurtz

powder method. Powder samples were sandwiched between glass plates, with a 58 F

gap,

and the temperature-dependent SHG signal was measured five times by comparison with sucrose. Temperature–dependent powder SHG measurement was conducted on glass substrate equipped with temperature controller and the SHG intensity was relative magnitude with granular sugar. Although the SHG intensity was not strong due to insufficient polar domain orientation in the absence of the application of electric filed and/or poling procedure, the SHG signal could be observed in the ferroelectric phase without the poling process through the phase transition from non-polar paraelectric to polar ferroelectric phase. A femtosecond pulsed beam (wavelength 1400 nm) from an optical ACS Paragon Plus Environment

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parametric amplifier (Spectra-Physics, OPA-800C) pumped by a beam from a Ti:sapphire regenerative amplifier (Spectra-Physics, Spitfire) was used as the light source. The pulse duration was typically 150–200 fs, and the repetition rate was 1 kHz. The average incident power was 0.2 mW. The incident beam was focused by a plano-convex lens (f = 120 mm). The output SHG signals at wavelength of 700 nm were detected by a photomultiplier tube (Hamamatsu, Model SR250) and processed using a boxcar average (Stanford Research, Model SR250).

3. Results and Discussion

Crystal 1 showed a reversible and successive phase transition of S1-S2 (solid-solid) at 338 K, S2-M (solid-mesophase) at 444 K, and M-I (solid-isotropic liquid) at 564 K based on the differential scanning calorimetry (DSC) trace (Figure 1a). The enthalpy change ( H) of the S1-S2 phase transition was of a ACS Paragon Plus Environment

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considerably small magnitude of 7.72 kJmol-1, suggesting a subtle structural change at approximately 338 K. In contrast, a fluidic behavior in the M phase was confirmed under a polarized optical microscope (POM) image in a cross-Nicol optical arrangement at 543 K, suggesting the formation of a typical liquid crystalline phase (Figure 1b). However, the relatively viscous behavior of the M phase corresponded to the formation of a high-ordered liquid crystalline phase. The thermogravimetric (TG) diagram of 1 indicated a considerably high thermal stability up to 640 K in the absence of weight loss because of the thermal decomposition (Figure S1). Before the decomposition, the liquid crystalline M phase melted at 564 K with H = 77.8 kJmol-1 and the isotropic liquid phase was thermally stable up to 640 K. Because the -framework of tetraphenylporphrin itself has a considerably high thermal stability up to 720 K, the

core is useful for the stable operation of organic flexible devices in a high

temperature environment. Absorption spectra of molecule 1 in CHCl3 indicated an intense Sore-band at 420 nm and multiple Q-bands at 516, 551, 591, and 646 nm (Figure S2), consistent with a typical porphyrin

core. An intense fluorescence band was observed at the two emission maxima at 652 and

720 nm with a quantum yield of 4.42% (Figure S2).

a)

b) T = 343 K

T = 543 K


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Figure 1. Thermal phase transition behavior of 1. a) Reversible and successive phase transitions of S1-S2, S2-M, and M–I in the DSC diagram. b) POM images of S2 phase at 343 K and M phase at 543 K in a cross-Nicol optical arrangement.

Figure 2 shows the temperature-dependent vibrational infrared (IR) spectra of 1 on the KBr pellet to evaluate the intermolecular N-H•••O= hydrogen-bonding interaction (Figure S3). Symmetrical and antisymmetrical C-H stretching vibrational modes of

s

respectively, whereas the N-H stretching mode (

NH)

at 298 K. The free

NH

CH

and

a CH

were observed at 2850 and 2920 cm-1,

was confirmed as approximately 3300 cm-1

mode and intermolecular N-H~O= hydrogen-bonding

NH

one of the

aromatic alkylamide derivative were typically observed at 3450 and 3250 cm-1, respectively. The energy of the free

NH

mode was approximately 200 cm-1 blue shift in contrast with that of

the intermolecular N-H•••O= hydrogen-bonding dependent change in the

NH

NH

mode. Figure 2b shows the temperature-

modes during the S1, S2, M, and I phases in the heating and

cooling cycle. The energies of the

NH

modes during the S1, S2, M, and I phases showed a

gradual blue shift to 3300, 3304, 3313, and 3321 cm-1, respectively, via an increase in the temperature and were reversibly observed in the thermal cycle. In addition, the energies of the vCO stretching and/or vNH bending modes during the S1, S2, M, and I phases were also


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observed at 1635, 1637, 1638, and 1640 cm-1, respectively (Figure S4). The energy changes of intermolecular N-H•••O= hydrogen-bonding each other. The blue shift of the

NH

NH

and

CO

stretching bands were coupled to

mode was consistent with the decrease in the force

constant of the intermolecular N-H•••O= hydrogen-bonding interaction at much higher temperatures. Weakly binding intermolecular N-H•••O= hydrogen bonds in the (1)C column enable a change in the orientation of the polar hydrogen-bonding unit.

a)

b)

T

Figure 2. Temperature-dependent vibrational IR spectra of 1 on the KBr pellet within the energy ranges of a) 400–4000 cm-1 and b) 3200–3400 cm-1.


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Temperature-dependent change in the molecular assembly structures of 1 was evaluated using the powder X-ray diffraction (PXRD) patterns of S1 at 293 K, S2 at 393 K, and the M phase at 523 K together with Colh phase of 3BC (Figure 3a). The PXRD measurements were observed in vacuum to avoid the contamination of crystalline domain, oxidation, and thermal decomposition, and the background PXRD pattern was also confirmed at high temperature (Figure S8). A sharp diffraction peak at 2 = 2.50° for the M phase was assigned to a d spacing of 3.534 nm, and the additional diffraction peaks at 2

= 5.42, 7.52, and 10.91°

corresponded to a d spacing of 1.631, 1.176, and 0.811 nm, respectively. When the lattice parameter of d100 = 3.534 nm was assumed to a (100) index of the hexagonal Colh phase, the characteristic diffraction peak of the d110 should be observed at d ~ 2.040 nm. However, the secondary intense diffraction peak at 2 = 5.42° corresponded to d = 1.631 nm, approximately 0.4 nm less than that of the ideal d110 distance of the hexagonal lattice. Therefore, the formation of the Colh phase was inconsistent with the molecular assembly structure of the present M phase. The M phase of 3BC clearly indicated both the diffraction peaks of (100) and (110) index, which could be safely assigned to Colh phase. In contrast, the assignment of a diffraction peak at 2

= 5.42° to the d020 index was consistent with the formation of a

rectangular lattice (Colr phase) at d020 = 1.631 nm, which was also consistent with the high order diffraction peak at 2 = 10.91° and at d040 = 0.811 nm. The lattice constants of a and b ACS Paragon Plus Environment

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axis for Colr lattice were 3.53 and 3.26 nm, respectively, which were consistent with the three diffraction peaks at (020), (200), and (040) index, respectively.

The maximum molecular

length assuming the all-trans alkyl chains (~4.8 nm) was much longer than the lattice parameters at d100 = 3.53 nm and d010 = 3.26 nm, suggesting melting and interdigitated states of the four –CONHC14H29 chains in the Colr phase. Therefore, the formation of a discotic rectangular columnar mesophase (Colr) is the most reasonable molecular assembly structure for the intermediate M phase of 1. A broad diffraction peak at approximately a 2 ~ 20° was also consistent with the melting state of the lateral –CONHC14H29 chains, which had been typically observed in a liquid crystalline state. However, several weak diffraction peaks were observed on the broad diffraction peak because of the formation of a rigid and ordered Color phase (Figure 3a). The highly ordered molecular assembly such as Color phase can be classified as a soft crystal with a breaking of inversion symmetry, which activated the SHG intensity and ferroelectricity. On the contrary, the intense broad diffraction peak at 2 ~ 20° has been observed in Colh phase of 3BC. The intensity ratio of (100) and broad (001) diffraction dependent on the orientation of each column on the substrate surface. When the columns were oriented along the direction parallel to the substrate surface, the intense (100) reflection should be observed in the PXRD pattern. On the contrary, the normal orientation of the columns to the sudbstrate surface suppressed the (100) reflection (3BC in Figure 3a). ACS Paragon Plus Environment

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Therefore, the


-stacking columns of 1 were oriented along the direction parallel to the

substrate surface, which increased the intensity of (100) peak and suppressed the (001) one. The low S/N diffraction pattern around 2 ~ 20° was due to the normal orientation of each column of 1. The cast-film of 1 on a highly ordered pyrolytic graphite (HOPG) substrate surface was fabricated using the drop-cast method with a CHCl3 solution. A mesoscale 1D molecular assembly with a typical width of several 100 nm and a length of several 100 m was observed on the substrate surface (Figure 3b), consistent with the 1D

-stacking structure via the

intermolecular N-H•••O= hydrogen-bonding interaction. Both the crystalline S1 and S2 phases showed sharp diffraction peaks at approximately a 2 ~ 3.0°, corresponding to d = 2.870 nm during the S1 phase and d = 2.916 nm during the S2 phases respectively. The appearance of sharp diffraction peaks within the overall measuring 2 -range was consistent with the highly ordered crystalline state of the S1 and S2 phases and nearly the same molecular assembly structures were assumed in both.


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Figure 4. Theoretical DFT calculation of a

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-stacking hydrogen-bonding dimer of a

tetaphenylporphyrin dimer bearing four –CONHCH3 groups. The optimized hydrogen-bonding dimer viewed along the direction a) normal and b) parallel to the -plane.

Figures 5 shows the T- and f-dependent real part ( 1) and imaginary part ( 2) dielectric constants of 1. Because the dielectric response was associated with the motion of a polar structural unit in the molecular assembly, the dynamics of the polar N-H•••O= hydrogen-bonding unit are observed in the Tand f-dependent dielectric constants. There was no dielectric anomaly around the S1-S2 phase transition temperature at approximately 338 K because of the subtle structural change of the polar unit. In contrast, a dielectric jump was observed around the S2-Colr phase transition temperature at approximately 444 K. During the Colr phase, both the

1

and

2

values were gradually enhanced by increasing the temperature

under a much lower measured f condition, suggesting the existence of thermally activated slow dipole motion. The T- and f-dependent

1

and

2

responses of 1 were similar to those of the ferroelectric 3BC

and 4PC. Figure 5c shows the f-dependent P-E hysteresis curves of 1 at 503 K during the Colr phase. The P-E hysteresis behaviors were confirmed in the measured f range from 0.1 to 1.0 Hz, where the ferroelectric parameters of Pr ~ 1 Ccm-2 and Ec = 1 V m-1 at f = 0.1 Hz were nearly consistent with those of 3BC and 4PC. In addition, the butterfly-shaped responses in the electric field-polarization current (E-I) curves were consistent with the ferroelectric behavior, in which the current response at f = 1 Hz was much higher than that at f = 0.5 Hz (Figure 5d). The magnitude of the total dipole moment for the four N-H•••O= hydrogen-bonding interactions with the same orientation was estimated to be

=

15.12 Debye. The theoretical polarization of approximately 1.07 Ccm-2 was nearly consistent with that of the experimental value of Pr ~ 1 Ccm-2. Temperature dependent second harmonic generation (SHG) ACS Paragon Plus Environment

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measurement at 500 K was consistent with the ferroelectricity in high temperature Colr phase (Figures S6 and S7). To confirm the absorption and resonance effects of incident and detection light, the diffusion reflection spectrum of 1 was measured in the solid state and the incident leaser wavelength of 1400 nm and detection photon at 700 nm were selected in the temperature dependence. The SHG active behavior was observed at 500 K in the absence of electric filed, which intensity was 10 % of that of the granulated sugar. The temperature decreasing to 423 and 373 K also indicated the SHG activity of 5 and 2 % ratio with that of granulated sugar, while the SHG activity was completely disappeared at 298 K. The dipole arrangement in high temperature Colr phase broken the inversion symmetry of molecular assembly and appeared the ferroelectric response. The time-dependent polarization curves of non ferroelectric phase at 298 and ferroelectric one at 503 K were measured to estimate the polarization state. The polarization was not observed at 298 K after the application of pulse voltage, while the polarization relaxation was confirmed at 503 K (Figure S9). The polarization relaxation was continued at least 10 sec, however, the leak current at high temperature measurement at 503 K affected the polarization behavior. Because the high-temperature ferroelectric P-E hysteresis curve at approximately 500 K can be applied to a high-temperature ON/OFF organic memory device, the thermally stable porphyrin framework becomes a useful memory candidate in the fabrication organic electronics operating in a high-temperature environment.


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a)

b)

c)

d)

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Figure 5. Dielectric and ferroelectric behaviors of 1. T- and f-dependent a) real part ( 1) and b) imaginary part ( 2) dielectric constants. c) Polarization – electric field (P – E) hysteresis curves at f = 0.1, 0.2, 0.5, and 1 Hz (T = 503 K). d) Butterfly-shaped polarization current – electric field (I - E) curves at f = 0.2, 0.5, 1.0, and 10 Hz (T = 503 K).

4. Conclusion

Multiple intermolecular hydrogen-bonding –CONHC14H29 chains were introduced into the tetraphenylporphyrin -framework (1) to form a ferroelectric columnar liquid crystalline material. The crystal 1 indicated the successive phase transitions of S1-S2 at 338 K, S2-Colr at 444 K, and Colr-I at ACS Paragon Plus Environment

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564 K, respectively. A discotic rectangular columnar Colr liquid crystal phase was observed via the aid of a -stacking porphyrin core and the intermolecular N-H•••O= hydrogen-bonding interaction along the column direction, whose molecular assembly structure was nearly similar to those of the ferroelectric 3BC and 4PC. The thermal stability of 1 was considerably high at the decomposition temperature of approximately 640 K based on the TG diagram because of the thermally stable porphyrin

-core.

Collective motion of the polar N-H•••O= hydrogen-bonding chains in the flexible molecular assembly of the Colr phase formed 1D ferroelectrics through dipole inversion of the direction of the hydrogenbonding chain. The T- and f-dependent dielectric constants

1

and

2

indicated an anomaly around the

S2-Colr phase transition temperature, indicating slow molecular motions of the polar structural unit during the Colr phase. Both the P-E and I-E curves at 503 K during the Colr phase indicated the hysteresis and butterfly-shaped responses, respectively, which were typically to the ferroelectric ground state. A high-temperature operational ON/OFF organic memory device could possibly be designed using the thermally stable porphyrin -core, showing a potential to fabricate a high-temperature flexible organic memory device.

ASSOCIATED CONTENT

Supporting Information. TG chart, absorption and fluorescence spectra in CHCl3, vibrational IR spectra at 298 K on KBr pellet, temperature dependent change in vibrational

C=O,

formation of

lyotropic liquid crystal phase in CHCl3, solid state diffuse reflection spectrum, temperature dependent SHG intensity change, temperature dependent PXRD pattern of glass substrate and 1, and time dependent polarization behaviors. This material is available free of charge via the Internet at http://pubs.acs.org.


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AUTHOR INFORMATION

Corresponding Author

* [email protected]

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS

This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas ‘ -Figuration’ (JP26102007), Kiban Kenkyu (A) (JP19H00886), Japan Science and Technology Agency CREST Grant Number JPMJCR18I4, and ‘Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials’ from the Ministry of Education, Culture, Sports, Science and Technology.

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