Covalently Bonded Pillared Layered Bromoplumbate with High

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Covalently Bonded Pillared Layered Bromoplumbate with High Thermal Stability: High Capacitance Gain after Photoinduced Electron Transfer Cai Sun, Ming-Sheng Wang, and Guo-Cong Guo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b06375 • Publication Date (Web): 01 Aug 2019 Downloaded from pubs.acs.org on August 4, 2019

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ACS Applied Materials & Interfaces

Covalently Bonded Pillared Layered Bromoplumbate with High Thermal Stability: High Capacitance Gain after Photoinduced Electron Transfer Cai Sun, Ming-Sheng Wang,* and Guo-Cong Guo* State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China

ABSTRACT: Improving stability and photoelectric properties are current aims in the field of inorganic-organic hybrid lead halides. In this work, a new covalently bonded pillared layered bromoplumbate, [Pb3Br6(CV)]n, was prepared using the photoactive zwitterion viologen N,N’-4,4’-bipyridiniodipropionate (CV) as a ligand. It has a high thermal stability in air, and showed a remarkable increase of capacitance after photoinduced electron transfer (PIET). The observed dielectric switch ratio of ~689% at 3 kHz exceeded all reported values at room temperature for switchable dielectric materials. The capacitance gain derived from the redistribution of electrons after PIET from lead halide layer to organic π-aggregates, so that the activation energy of hopping polarizability significantly reduced. KEYWORDS: capacitance gain, dielectric switch, electron transfer, inorganic-organic hybrid, , photochromism,

INTRODUCTION In recent years, barriers to traditional organic and inorganic chemistry have been broken. In the new family of hybrid lead halides, many materials have superior performance over traditional inorganic materials.1-4 For example, the lead-halide perovskite has become a recent black horse in the field of solar cells for high power conversion eﬃciency comparable to commercial multicrystalline Si cells.5-7 Designing and synthesizing new structures to achieve superior performance is a never-ending issue for chemists. From a crystallographic point of view, the introduction of organic molecules into inorganic perovskite structures greatly increased the diversity of structures. The lead halides unit can construct various dimensions of structures such as 0D, 1D, 2D to 3D by means of co-vertex, co-edge, and co-planar connection.5, 8-10 In all these known structures, each Pb atom formed an octahedral coordination pattern with the surrounding six halogen atoms, and the organic ammonium salt and inorganic components were interacted with each other through ionic bonds, hydrogen bonds, and van der Waals. Nevertheless, these perovskites featured the poor long-term stability against light, heat, and moisture. Covalently bonding between organic and inorganic components not only significantly improves the stability, but provides possibilities to develop new structures and functions for hybrid lead halides. For example, in our previous work, we successfully connected Pb atoms with O atoms from organic ligands through covalent bonds.11 The addition of heteroatoms broke the configuration of the lead halide octahedron and formed a richer coordination mode, such as distorted bi- or tricapped trigonal prism polyhedra. This structure exhibited

long-term stability against light and moisture, and its electrical conductivity and photocurrent greatly improved after photoirradiation. The covalently bonded strategy opens a new avenue for improving the stability and functionality of hybrid lead halides using in some severe environments. Materials with high dielectric constant are widely used in large capacity capacitors.12-14 This application places high demands on the stability of the material due to the long-term charging and discharging process. Moreover, a high dielectric constant can increase the capacitance of the capacitor, making the volume of capacitor smaller at the same capacity. Therefore, it is meaningful to design and synthesize materials with high stability and high dielectric constants.15 To date, most documented approaches to improve capacitance are highly empirical and have met with limited success.12 For instance, the capacitance can be improved 2 times by altering the building block donor, acceptor, or bridge structures in the donor−bridge−acceptor molecule systems.12 Compared with these chemical methods, physical methods such as irradiation and heating are more convenient to modify the capacitance properties without altering components or structures. From the microscopic point of view, relative dielectric permittivity (εr) closely relates to polarizability (α): εr = 1 + α/ε0, where ε0 is vacuum permittivity. Polarizability strongly related to the distribution of positive and negative charges. Localized electric charges can hop from one site to the neighboring site to form a dipole, creating the so-called hopping polarization.16 Inspired by the re-distribution of charges during the electron transfer photochromic process,17 we proposed that the active electric charges could increase hopping

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polarizability after photoinduced electron transfer (PIET), then improve the dielectric permittivity. In addition, inorganic-organic hybrid pillared layered structure can form a significant space charge polarization at low frequency ac electric field due to the interfacial contact between the inorganic layer and the organic component, and thus may show a higher dielectric permittivity than the parent inorganic material.13, 18 To achieve a covalently bonded pillared layered lead halide with PIET behavior, we adopted the doubly bridging viologen ligand with redox photochromic activity, N,N’-4,4’bipyridiniodipropionate (CV), as a ligand, and

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successfully obtained an inorganic-organic hybrid pillared layered bromoplumbate, [Pb3Br6(CV)]n (1), where 2-D [Pb3Br6]n layers connect with 1-D organic CV π-aggregates by covalent bond (Figure 1). It shows high heat stability, and an ET photochromic behavior between the inorganic and organic components. After PIET, its capacitance increased about 8 times at 3 kHz. This is the first example of modifying capacitance through PIET. Moreover, the dielectric switch ratio (~689% at 3 kHz) exceeded all reported switchable dielectric materials at room temperature (RT).19-24

Figure 1. Crystal structure of 1. a-c) Structural evolution of the pillared layered structure. Hydrogen atoms are omitted for clarity.

EXPERIMENTAL SECTION Materials and Instrumentation. PbBr2, 4,4’-bipyridine, and acrylic acid of AR grade were purchased and used without further purification. Water was used after deionizing and distilling. Elemental analyses were conducted on an Elementar Vario EL III microanalyzer. Fourier transform infra-red spectroscopy (FT-IR) patterns were recorded on a PerkinElmer Spectrum One FT-IR spectrometer using KBr pellets. Electronic absorption spectra were recorded on a PerkinElmer Lambda 900 UV/vis/near-IR spectrophotometer equipped by the diffuse reflectance mode with an integrating sphere, and a barium sulfate plate was used as the reference. Powder X-ray diffraction (PXRD) data were measured on a Rigaku Desktop MiniFlexII diffractometer at 30 kV and 15 mA with Cu Kα radiation (λ = 1.54056 Å). Simulated pattern was produced by using the Mercury program and the single crystal X-ray diffraction (SXRD) data. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) data were recorded on a Mettler TOLECO simultaneous TGA/DSC apparatus in nitrogen atmosphere with the ramp rate of 10 °C/min. Electron spin resonance (ESR) data were conducted on a Bruker ER-420 spectrometer in the X band with a 100 kHz magnetic field. Complex dielectric permittivities of pellet samples were measured under a vacuum environment in a probe station (Lake Shore CRXVF) using an Agilent 4294A impedance analyzer with an applied electric field of 10 V over the frequency range of from 0.5 to 100 kHz. The dc conductivities were recorded in a Keithley 4200-SCS semiconductor parameter analyzer under a vacuum environment using pellet samples with silver paste on the two probe. The dc conductivities and complex dielectric permittivities before and after coloration were realized by in situ illumination using the 300 W Xe lamp.

Synthesis CV and {[Pb3Br6(CV)]}n (1). CV was synthesized by our previous reported procedure.11 After stirring PbBr2 (367 mg, 1 mmol) and CV (300 mg, 1 mmol) in 25 ml water at 70° for four hours, the orange red precipitations can be generated, then re-crystallized with water and allowed to volatilize in the dark for 1 week to obtain the red sheet crystalline samples. Yield: 67.9% (based on Pb). The phase purity of their crystalline samples of 1 was checked by PXRD (Figure 2a) and elemental analyses. Anal. Calcd for 1: C, 13.71; H, 1.15; N, 2.00%. Found: C, 13.57; H, 1.21; N, 1.95%. FT-IR (KBr, 4000−400 cm−1) 3091 (w), 3029 (m), 2954 (w), 1635 (m), 1552 (s), 1495 (w), 1442 (w), 1423 (s), 1350 (w), 1313 (m), 1283 (w), 1222 (m), 1197 (m), 1160(w), 1007 (w), 950 (w), 887 (m), 830 (s), 717 (w), 617 (m), 572 (w), 501 (w) (Figure 2b). X-ray crystallographic study. SXRD data for a same single crystal of 1 before and after coloration were conducted on a Rigaku Pilatus 200K diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at 293 K. The colored sample (1B) was illuminated with a 300 W Xe lamp (ca. 50 mW/cm2) for 180 min. Intensity data sets were collected through ω-scan technique, and corrected for Lorentz and polarization effects. The structures were solved by the direct method using the SHELXTLTM software.25 Other non-hydrogen atoms were derived from the difference Fourier map. Hydrogen atoms were added geometrically and refined using the riding model. The final structures were refined using a full-matrix least-squares on F2 with anisotropic thermal parameters for all non-hydrogen atoms. Crystal data and structure refinement results for 1 is summarized in Table 1. The detailed comparison of bond lengths and bond angles are listed in Table S1 and S2 in the Supporting Information (SI).


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ACS Applied Materials & Interfaces Table 1. Crystal and structure refinement data for 1 1A (assynthesized)

1B (colored)

Formula

C16H16O4N2Br6P b3

C16H16O4N2Br6 Pb3

Mr

1401.34

1401.34

Crystal size

(mm3)

0.07 × 0.06 × 0.02

Crystal system

Monoclinic

Monoclinic

Space group

C2/c

C2/c

a (Å)

25.1351(12)

25.1361(6)

b (Å)

4.6642(2)

4.6632(2)

c (Å)

23.7112(12)

23.7066(7)

 (deg)

114.438(4)

114.459(2)

2530.7(2)

2529.39(15)

Dcalcd (g/cm3)

3.678

3.680

Z

4

4

F(000)

2456

2456

Abs coeff (mm–1)

29.408

29.424

Reflns collcd/unique (Rint)

26024/2576 (0.0502)

27216/2574 (0.0507)

Data/params/restrai nts

2576/141/0

2574/141/0

R1 a

0.0309

0.0309

ωR2b

0.0716

0.0717

GOF on F2

1.168

1.180

∆max/∆min (e/Å3)

2.21/-1.27

2.11/-1.31

V

aR 1

(Å3)

The phase purity of compound 1 was verified by elemental analysis, PXRD (Figures 2a) and FT-IR data (Figures 2b). TGA (Figure 2c) and PXRD data (Figure 2a) exhibited that 1 was stable at least up to 180 °C. The PXRD patterns also showed that 1 was stable against moisture. The TGA curve of 1 exhibited two-step weight loss of 10.6%from 250 to 280 °C and 10.2% from 280 to 350 °C with sharply endothermic peaks at 264.5 °C and 335.4 °C in the DSC curve, respectively. These data showed that the total weight loss of 20.8% could be related to the decomposition of CV (calcd: 20.1%) and sublimation (Figure 2c). Compound 1 exhibits an inorganic−organic hybrid pillared layered structure, where 2-D inorganic [Pb3Br6]n monolayer connects to 1-D organic π-aggregates by Pb-O bonds (Figure 1). Two crystallographically independent Pb atoms (Pb1 and Pb2) are in the 2-D inorganic monolayer (Figures 1a and 1b). The Pb1-centered [PbBr6] octahedra connect with each other through edge sharing to form an infinite chain extending along the b direction. Every Pb2 atom is coordinated by five Br atoms to form a distorted [PbBr5] square pyramid. These square pyramids connect with each other by edge-sharing to yield a single chain, which further edge-share with its symmetry-related chain to form a double chain extending along the b axis. Each Pb1-centered single chain bridges the Pb2-centered double chains through edge-sharing the polyhedra along the a direction to generate a [Pb3Br6]n layer in the ab plane. Finally, Pb2-centered [PbBr5] square pyramid connects with three O atoms from two CV ligands by PbO bonds to form a bicapped trigonal prism polyhedron, and finishes the 3-D pillared layered structure. Notably, the distance between each N+ atom and its neighboring pyridinium plane is 3.56(2) Å between adjacent CV, which shows strong cation−π interactions.

= Fo–Fc/Fo, bωR2 = {ω[(Fo)2–(Fc)2]2/ω[(Fo)2]2}1/2.

Computational approaches. Calculation model was based on the crystallographic data of 1. The Vienna ab initio Simulation Package (VASP) code on the basis of density functional theory (DFT) was used to calculate the charge density with the projector-augmented-wave potential.26-27 In order to consider the weak van der Waals between inorganic and organic components, the Perdew−Burke−Ernzerhof exchange-correlation functionals with an optB86b-vdW correction was used.28-29 The plane-wave cutoff energy was set as 400 eV. The k-points were set as Monkhorst–Pack grid with 1  5  1. Charge density difference calculations were conducted on the basis of the following equation: Δ𝜌 = 𝜌𝐴𝐵 – 𝜌𝐴– 𝜌𝐵, where 𝜌𝐴𝐵 was the total electron density of 1, and 𝜌𝐴 and 𝜌𝐵 were, respectively, correspondingly total electron densities of the inorganic layers and CV cations. Figure 2f on charge density difference was plotted using the VESTA package.30

RESULTS AND DISCUSSION



the cell in 1 with yellow and blue isosurface levels being set at ±0.003 a0−3 (a0 is the Bohr radius).

Figure 2. a) Experimental (Exp) and simulated (Simu) PXRD patterns of 1. The time for heat-treatment at both 120 °C and 180 °C were 2 h. The moisture-resistant test was conducted with a relative humidity (RH) of 100% and a period of 7 d. b) FT-IR spectra of 1. c) TGA and DSC curves of 1 in nitrogen atmosphere with the ramp rate of 10 °C/min. d) Timedependent absorption spectra of 1 upon irradiation. Inset: Color change in the photochromic process. e) First derivative EPR spectra of 1. f) Isosurfaces of charge density difference of

Compound 1 possessed photochromism. As shown in Figure 2d, the as-synthesized crystalline sample of 1 changed from red to reddish black when illuminated with a Xe lamp. PXRD (Figures 2a) and IR (Figures 2b) data revealed no clear structural change after coloration. SXRD measurements of the same single crystal before and after coloration revealed that the differences in geometry were only minor or negligible (Tables 1, S1 and S2). The 1B showed a characteristic absorption band covering the 500−1000 nm region (Figure 2d), which was characteristic of the one-electron reduced species of the viologen based compounds.11, 31 The photoinduced coloration tended to be saturated after irradiated for 180 min. No ESR signals existed before coloration (Figure 2e); however, after coloration, a radical signal appeared at g = 2.0014 with a line width of 9 G. Thus, the absorption spectra and ESR data verified that PIET occurred during the coloration process of 1. A charge density difference calculation provided insight into the photochromic behavior of 1. As shown in Figure 2f, the charge densities of the Br atoms in the inorganic framework and carboxylate O atoms increased, but that of 4,4’-bipyridinium (bpy) cations decreased owing to the interactions between inorganic and organic components. This result implies that Br and O atoms and bpy cations tended to donate and accept electrons after photoinduced coloration, respectively. The photoproduct 1B can be retained in air at RT for several weeks. After annealing at 60 °C in O2 for 1 d, the initial red color was regained (Figure 2d and S2) with missing radical signal (Figure 2e).

Figure 3. a) Schematic of the experimental setup as a photoswitching variable capacitor. b) Time-dependent capacitance (Cr) upon irradiation, and capacitance gain ratio at different frequencies. c-d) Time-dependent ε’ and ε’’ of 1 upon irradiation as a function of frequency. e) Time-dependent relaxation time (τ) of hopping polarization upon irradiation. f) Temperaturedependent dc conductivities of 1 before and after coloration. g) Schematic of a double potential well showing the formation of the hopping polarization.

Bulk capacitance tests of 1 were investigated by ac field with frequency (f) from 0.5 to 100 kHz in a parallel-plate capacitor model (electrode area S = 0.5 mm2, sample length d = 2 mm) using silver paste as electrodes under

vacuum at RT (Figure 3a). As shown in Figure 3b, capacitances (Cr) changed under different frequency ac field, and reduced as increasing frequency. The Cr values increased with increasing irradiation time, and tended to


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ACS Applied Materials & Interfaces be saturated after irradiating for 12 hours. As the frequency increased, the ratio of capacitance gain raised first and then decreased, and the capacitance value gain ratio reached the maximum (~8 times, Figure 3b) from 0.043 pF to 0.345 pF at about 3 kHz. This phenomenon indicated the application prospect of the hybrid pillared layered bromoplumbate as a light-controlled variable capacitor. To understand the reason for the capacitance gain after irradiation, the complex relative dielectric permittivity (ε = ε’ − jε’’, where ε’ and ε’’ are real and imaginary parts, respectively) was studied. As depicted in Figure 3c, the ε’ values of 1 increased as irradiation time was prolonged, and variation at frequencies range of 0.5 to 10 kHz was pronounced. When saturation was reached, the maximum dielectric switch ratio, (Δε’/ε’(0))max, was approximately increasing 689% at 3 kHz, where Δε’ = ε’(irradiation time) − ε’(0), and the ε’ values increased from 19.7 to 155.3 (Figure S3). The dielectric gain exceeded all reported switchable dielectric materials at RT (Figure S4).19, 32-33 In general, the total polarizability (α) of a material with f from 0.5 to 100 kHz mostly comprises four components, α = αe + αi + αo + αh, where αe, αi, αo, and αh are the polarizabilities due to electronic, atomic, orientational, and hopping polarizations, respectively.16 The relaxation time for αe and αi is so short to be assumed to be constant at test frequencies from 0.5 to 100 kHz, and the change of αo related to the change of temperature associated with a dynamic dipolar change, so the increase of ε’ values after irradiation from 0.5 to 100 kHz mainly originated from the hopping polarization. Moreover, the ε’ values almost remained constant on irradiation time above 100 kHz (Figure 3c), and the relaxation time required for αh is usually longer than 0.1 μs (100 kHz). These data also demonstrated that the change of ε’ values originated from the hopping polarization. The imaginary part ε’’ can be used to describe a dielectric material's inherent loss of energy under an ac electric field. As shown in Figure 3d, the ε’’–f curves at all measured irradiation times are peak-shaped, with the frequencies of peak maxima shifting progressively towards high frequency with increasing irradiation time. According to the Debye relaxation model,16 the relaxation time (τ0) can be gotten from the reciprocal of frequency corresponding to the maximal loss value. Figures 3e showed that the τ0 of αh shortened from 0.98 ms to 1.4 μs after irradiation, indicating that additional hopping dipoles can be built in the unit time. As depicted in an ideal, symmetrical double-well potential (Figure 3f), a charge jumps, surmounting a potential barrier to other sites to form a hopping dipole, depending on the width (r) and the height (Ea) of the potential barrier. The hopping probability (p0) for a hopping dipole can be written as p0 = Ae - Ea/kT, where Ea is also called activation energy for the electron hopping between two adjacent potential wells, and A and k are pre-exponential factor and Boltzmann constant,

respectively. The αh associated with p0 can be expressed as αh = q2r2p02/3kT, where q is the unit electric charge. Thus, αh can be changed by changing the Ea, and the dielectric constant can then be adjusted. The dc electrical conductivity for a semiconductor is governed by thermal activation. The activation energy, which is related to electron hopping between two adjacent potential wells, can be estimated from the Arrhenius equation σ = Be - Ea/kT, where σ and B are dc electrical conductivity and pre-exponential factor, respectively.34-35 Bulk electric tests for pressed sample of 1 was also investigated in vacuum by the two-probe method using silver paste. The symmetric linearity of the current–voltage (I–V) characteristic curves at 298 K for the same pellet sample before and after coloration (Figures S5) exhibited the formation of an Ohmic contact between silver paste and the sample. The dc electrical conductivity measure within temperature range of 270−320 K followed the Arrhenius equation (Figures 3g). The linear relationship of the natural logarithm of σ versus 1/T showed that compound 1 behaved as intrinsic semiconductor.36 The electric activation energy of 1 fell dramatically from 0.24 to 0.15 eV after coloration. These results showed that the activation energy of hopping transition decreases after PIET, leading to additional hopping dipoles, and then increasing the hopping polarizability and dielectric permittivity.

CONCLUSIONS In summary, we have prepared a viologen-modified lead halide hybrid with a novel 3-D pillared layered framework by a covalently bonded strategy, and succeeded in observing an electon transfer photochromism and capacitance gain after irradiation for the first time. The increase of capacitance value derived from the redistribution of electrons after PIET, so that the activation energy of the hopping polarizability was significantly reduced. This work not only demonstrates the effectiveness to obtain more functional lead halide hybrids through a covalently bonded strategy, but also provides a new avenue for smart electronic components, such as light-controlled variable capacitors.

ASSOCIATED CONTENT Supporting Information X-ray crystallographic data for 1A and 1B with the entries of CCDC-1935482 and 1935483, respectively. Bond lengths and bond angles of 1A and 1B, structural formula of CV, absorption spectra of decolored sample, dielectric switch ratio data, dc electrical studies of 1A and 1B. Supporting information is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected]

Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21601185), the program of CAS (QYZDB-SSW-SLH020), the National Postdoctoral Program for Innovative Talents (BX20180304), the Postdoctoral Program of China (2018M642580), and the Natural Science Foundation of Fujian Province (2017J01033, 2018J01028).

REFERENCES (1) Mitzi, D. B. In Progress in Inorganic Chemistry, Vol 48, Karlin, K. D., Ed. 1999, Vol. 48, pp 1-121. (2) Kagan, C. R.; Mitzi, D. B.; Dimitrakopoulos, C. D. Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors. Science 1999, 286, 945-947. (3) Wei, W.; Zhang, Y.; Xu, Q.; Wei, H.; Fang, Y.; Wang, Q.; Deng, Y.; Li, T.; Gruverman, A.; Cao, L.; Huang, J. Monolithic Integration of Hybrid Perovskite Single Crystals with Heterogenous Substrate for Highly Sensitive X-ray Imaging. Nat. Photonics 2017, 11, 315-321. (4) Cho, H. C.; Jeong, S. H.; Park, M. H.; Kim, Y. H.; Wolf, C.; Lee, C. L.; Heo, J. H.; Sadhanala, A.; Myoung, N.; Yoo, S.; Im, S. H.; Friend, R. H.; Lee, T. W. Overcoming the Electroluminescence Efficiency Limitations of Perovskite Light-Emitting Diodes. Science 2015, 350, 1222-1225. (5) Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells. J. Am. Chem. Soc. 2009, 131, 6050-6051. (6) Bella, F.; Griffini, G.; Correa-Baena, J. P.; Saracco, G.; Gratzel, M.; Hagfeldt, A.; Turri, S.; Gerbaldi, C. Improving Efficiency and Stability of Perovskite Solar Cells with Photocurable Fluoropolymers. Science 2016, 354, 203-206. (7) Jeon, N. J.; Noh, J. H.; Yang, W. S.; Kim, Y. C.; Ryu, S.; Seo, J.; Seok, S. I. Compositional Engineering of Perovskite Materials for HighPerformance Solar Cells. Nature 2015, 517, 476-480. (8) Dohner, E. R.; Hoke, E. T.; Karunadasa, H. I. Self-Assembly of Broadband White-Light Emitters. J. Am. Chem. Soc. 2014, 136, 17181721. (9) Zhou, C.; Tian, Y.; Wang, M.; Rose, A.; Besara, T.; Doyle, N. K.; Yuan, Z.; Wang, J. C.; Clark, R.; Hu, Y.; Siegrist, T.; Lin, S.; Ma, B. Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation. Angew. Chem. Int. Ed. 2017, 56, 9018-9022. (10) Zhou, C.; Lin, H.; Worku, M.; Neu, J.; Zhou, Y.; Tian, Y.; Lee, S.; Djurovich, P.; Siegrist, T.; Ma, B. Blue Emitting Single Crystalline Assembly of Metal Halide Clusters. J. Am. Chem. Soc. 2018, 140, 1318113184. (11) Sun, C.; Xu, G.; Jiang, X. M.; Wang, G. E.; Guo, P. Y.; Wang, M. S.; Guo, G. C. Design Strategy for Improving Optical and Electrical Properties and Stability of Lead-Halide Semiconductors. J. Am. Chem. Soc. 2018, 140, 2805-2811. (12) Heitzer, H. M.; Marks, T. J.; Ratner, M. A. Molecular Donor-BridgeAcceptor Strategies for High-Capacitance Organic Dielectric Materials. J. Am. Chem. Soc. 2015, 137, 7189-7196. (13) Everaerts, K.; Emery, J. D.; Jariwala, D.; Karmel, H. J.; Sangwan, V. K.; Prabhumirashi, P. L.; Geier, M. L.; McMorrow, J. J.; Bedzyk, M. J.; Facchetti, A.; Hersam, M. C.; Marks, T. J. Ambient-Processable High Capacitance Hafnia-Organic Self-Assembled Nanodielectrics. J. Am. Chem. Soc. 2013, 135, 8926-8939. (14) Sangwan, V. K.; Jariwala, D.; Filippone, S. A.; Karmel, H. J.; Johns, J. E.; Alaboson, J. M.; Marks, T. J.; Lauhon, L. J.; Hersam, M. C. Quantitatively Enhanced Reliability and Uniformity of High-Kappa Dielectrics on Graphene Enabled by Self-Assembled Seeding Layers. Nano Lett 2013, 13, 1162-1167. (15) Ha, Y. G.; Everaerts, K.; Hersam, M. C.; Marks, T. J. Hybrid Gate Dielectric Materials for Unconventional Electronic Circuitry. Acc. Chem. Res. 2014, 47, 1019-1028.

(16) Kao, K. C., Dielectric Phenomena in Solids: with Emphasis on Physical Concepts of Electronic Processes. Academic Press: 2004. (17) Bouas-Laurent, H.; Durr, H. Organic Photochromism. Pure Appl. Chem. 2001, 73, 639-665. (18) Zhang, X.; Hejazi, M.; Thiagarajan, S. J.; Woerner, W. R.; Banerjee, D.; Emge, T. J.; Xu, W.; Teat, S. J.; Gong, Q.; Safari, A.; Yang, R.; Parise, J. B.; Li, J. From 1D Chain to 3D Network: A New Family of Inorganic– Organic Hybrid Semiconductors MO3(L)x (M = Mo, W; L = Organic Linker) Built on Perovskite-like Structure Modules. J. Am. Chem. Soc. 2013, 135, 17401-17407. (19) Shang, R.; Wang, Z. M.; Gao, S. A 36-fold Multiple Unit Cell and Switchable Anisotropic Dielectric Responses in an Ammonium Magnesium Formate Framework. Angew. Chem. Int. Ed. 2015, 54, 25342537. (20) Zhang, W.; Cai, Y.; Xiong, R. G.; Yoshikawa, H.; Awaga, K. Exceptional Dielectric Phase Transitions in a Perovskite-Type Cage Compound. Angew. Chem. Int. Ed. 2010, 49, 6608-6610. (21) Goto, T.; Kimura, T.; Lawes, G.; Ramirez, A. P.; Tokura, Y. Ferroelectricity and Giant Magnetocapacitance in Perovskite Rare-Earth Manganites. Phys. Rev. Lett. 2004, 92, 257201. (22) Hur, N.; Park, S.; Sharma, P. A.; Guha, S.; Cheong, S. W. Colossal Magnetodielectric Effects in DyMn2O5. Phys. Rev. Lett. 2004, 93, 107207. (23) Bonhommeau, S.; Guillon, T.; Lawson Daku, L. M.; Demont, P.; Sanchez Costa, J.; Letard, J. F.; Molnar, G.; Bousseksou, A. Photoswitching of the Dielectric Constant of the Spin-Crossover Complex [Fe(L)(CN)2]H2O. Angew. Chem. Int. Ed. 2006, 45, 1625-1629. (24) Shimayama, K.; Karim, M. R.; Amolegbe, S. A.; Nakaya, M.; Nakamura, M.; Ohtani, R.; Lndoy, L. F.; Hayami, S. Photoswitching of the Dielectric Property of Salicylideneaniline. J. Inclusion Phenom. Macrocyclic Chem. 2015, 82, 219-223. (25) Siemens, SHELXTLTM Version 5 Reference Manual. Inc., S. E. A., Ed. Madison, Wisconsin, USA, 1994. (26) Perdew, J. P.; Burke, K.; Wang, Y. Generalized Gradient Approximation for the Exchange-Correlation Hole of a Many-Electron System. Phys. Rev. B 1996, 54, 16533-16539. (27) Hafner, J. Ab-initio Simulations of Materials Using VASP: DensityFunctional Theory and Beyond. J. Comput. Chem. 2008, 29, 2044-2078. (28) Klimes, J.; Bowler, D. R.; Michaelides, A. Chemical Accuracy for the Van der Waals Density Functional. J. Phys.-Condes. Matter 2010, 22, 022201. (29) Klimes, J.; Bowler, D. R.; Michaelides, A. Van der Waals Density Functionals Applied to Solids. Phys. Rev. B 2011, 83, 195131. (30) Momma, K.; Izumi, F. VESTA: a Three-Dimensional Visualization System for Electronic and Structural Analysis. J. Appl. Crystallogr. 2008, 41, 653-658. (31) Vermeulen, L. A.; Thompson, M. E. Stable Photoinduced Charge Separation in Layered Viologen Compounds. Nature 1992, 358, 656-658. (32) Liu, J. Y.; Zhang, S. Y.; Zeng, Y.; Shu, X.; Du, Z. Y.; He, C. T.; Zhang, W. X.; Chen, X. M. Molecular Dynamics, Phase Transition and Frequency-Tuned Dielectric Switch of an Ionic Co-Crystal. Angew. Chem. Int. Ed. 2018, 57, 8032-8036. (33) Shao, X. D.; Zhang, X.; Shi, C.; Yao, Y. F.; Zhang, W. Switching Dielectric Constant Near Room Temperature in a Molecular Crystal. Adv. Sci. 2015, 2, 1500029. (34) Chen, L. H.; Guo, J. B.; Wang, X.; Dong, X. W.; Zhao, H. X.; Long, L. S.; Zheng, L. S. Giant Room-Temperature Magnetodielectric Response in a MOF at 0.1 Tesla. Adv. Mater. 2017, 29, 1702512. (35) Barroso-Bogeat, A.; Alexandre-Franco, M.; Fernandez-Gonzalez, C.; Sanchez-Gonzalez, J.; Gomez-Serrano, V. Temperature Dependence of dc Electrical Conductivity of Activated Carbon-Metal Oxide Nanocomposites. Some Insight into Conduction Mechanisms. J. Phys. Chem. Solids 2015, 87, 259-270. (36) Grosso, G.; Parravicini, G. P. In Solid State Physics, 2nd ed.; Grosso, G.; Parravicini, G. P., Eds. Academic Press: Amsterdam, 2014, pp 577608.


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