Semiconducting OrganicâInorganic Hybrid Material with Distinct

Subscriber access provided by University of South Dakota

C: Plasmonics; Optical, Magnetic, and Hybrid Materials

A Semiconducting Organic-Inorganic Hybrid Material with Distinct Switchable Dielectric Phase Transition Tie Zhang, Cheng Chen, Wan-Ying Zhang, Qiong Ye, and Da-Wei Fu J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b06538 • Publication Date (Web): 26 Aug 2018 Downloaded from http://pubs.acs.org on August 26, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 19 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

The Journal of Physical Chemistry

A Semiconducting Organic-Inorganic Hybrid Material with Distinct Switchable Dielectric Phase Transition Tie Zhang, Cheng Chen, Wan-Ying Zhang, Qiong Ye*, Da-Wei Fu* (Ordered Matter Science Research Center, Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University, Nanjing, 211189, P.R. China) E-mail: [email protected], [email protected].

1

ACS Paragon Plus Environment

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

Page 2 of 19

Abstract: Hybrid materials such as CH3NH3PbI3 have led to significant attention due to their great properties are promising potential application in photovoltaic, optoelectronic devices, and sensing. However, there is a huge challenge to realize the dielectric switching/ferroelectricity and semiconducting attribute for these materials simultaneously. Modifying the halogen/metal and even controlling the dimensionality of the inorganic framework provides the possibility to obtain new or high-performance functional materials. Here we designed a hybrid compound: [(CH3)3NOH]2BiCl5, which shows remarkable dielectric switching properties at Tc = 183.5 K and semiconducting behavior with an optical bandgap of ∼3.225 eV. Experimental analysis revealed that the synergistic effect of microstructure of organic cations

and

inorganic

frameworks

contribute

to

the

multi-featured.

The

implementation of switching and semiconducting properties in the material has essential significance for expanding research on hybrid materials and the development of dielectric-optoelectronic integration devices.

2


Page 3 of 19 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


INTRODUCTION Hybrid compounds assembled by the inclusion of inorganic and organic components, have promoted rapid progress in optoelectronics and photovoltaics.1-4 Just as CH3NH3PbI3 perfectly illustrates the excellent optical, electrical and optoelectronic properties of hybrid materials.5-7 In addition, the hybrid materials with the preeminent semiconducting properties mainly promoted by the electronic structures of unique inorganic framework have been known by systematic experimental and theoretical calculations.8 And in previous work, researchers have realized the bandgap of semiconductors tuned over a wide range of energy by modifying the halogen or metal and even controlling the dimensionality of the inorganic framework. From hybrids materials of Sn(Ⅱ) or Pb(Ⅱ)-based to Cd(Ⅱ), Sb(Ⅲ) and Bi(Ⅲ)-based, a series of excellent materials have been reported.7, 9-14 Bandgaps of these materials are between 2 eV to 5 eV, which provide possibilities for the use of optoelectronic devices in different environments and different functional requirements. The switchable material for which physical characteristics such as dielectric, magnetic and optical, etc. responses are reversibly converted in diverse states by the stimulation of extra factors like temperature, light and electric fields, named as “switches”.15-21 And for we all know, of which these materials with ferroelectricity or dielectric switches which were converted between high and low dielectric states are promised applied in sensing, phase shifters and data communication have become research hotspot.22-25 Furthermore, research on the dielectrics has shown that the tunable dielectric is attributed to the positional freedom in the liquid state are larger than in the solid state due to the motion of molecules or ions in “melting” and “freezing”. Concerning organic-inorganic hybrid materials, integrating flexible units into the stable inorganic-frame to exhibits different states by thermal stimulus just like the behaviors of molecules/ions from solid to liquid state has evolved into an effective method to design dielectric switches.26,

27

For instance, the switchable material

(1-methylpiperidinium)PbI3 reported by Luo et al.28 3



Based on above, hybrid materials compared to conventional inorganic materials or organic salts have more potential to be multifunctional materials by utilizing the synergistic effect of organic cations and inorganic frameworks. Shortly before scientists have been aware of the possibility of their application in optoelectronic devices and diverse hybrid materials have been found.29-34 Nonetheless, it is essential in designing novel hybrid materials with multi-functionality because of lacking the competitive alternatives in low-cost/toxicity multi-function photoelectric devices. Herein, we present a novel switchable dielectric hybrid compound--(TMNO)2BiCl5 (1; TMNO=(CH3)3NOH), that shows semiconducting behavior with a bandgap (Eg) of ~ 3.225. In which the polar cations exhibit order-disorder in the space enclosed by anionic zigzag chains of [BiCl5]n, leading to striking dielectric anomalies around Tc = 183.5 K. Overall, this finding not only enriches the content of application of hybrid materials in optoelectronics and switching but provides a feasible way to explore new multifunctional materials for dielectric-optoelectronic integrated devices.

EXPERIMENTAL SECTION Synthesis. All of the chemical reagents were obtained from commercial sources and used without further purification. Single crystalline (TMNO)2BiCl5 (1) was prepared by slow solution evaporation of precursor solutions containing BiCl3 (3.15 g, 10 mmol), Trimethylamine N-oxide dehydrate (2.27 g, 20 mmol) and 36 % HCl (2.02 g 20 mmol) aqueous solution at room temperature. The phase purity of compound 1 was confirmed by powder XRD, which matches well with the simulated patterns of single crystal XRD structural data (Figure S1). The Powder X-ray diffraction (PXRD) patterns were obtained on a Rigaku SmartLab X-ray diffraction instrument. In the IR spectra of 1 (Figure S2), several vibration peaks at approximately 3525 cm-1, 1617 cm-1 and 1120 cm-1 are ascribed to stretching vibration absorption of the O-H, N-O and C-N bond respectively, indicating the existence of Trimethylamine N-oxide (TMNO) cation in 1. Furthermore, the stability of 1 was proved by its Thermogravimetric analysis (TGA) curve when it below 480 K (Figure S3).

4


Page 4 of 19

Page 5 of 19 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


Single-crystal X-ray Crystallography. Variable-temperature single-crystal X-ray diffraction data were collected on a Rigaku Saturn 924 diffractometer with Mo-Kα radiation (λ = 0.71073 Å) at 143 K and 293 K by ω scan mode. The data collections including empirical absorption corrections were performed with the CrystalClear software package. The crystal structures were solved by direct methods and refined with a full-matrix least-squares method based on F2 data with the SHELXTL software package. All non-hydrogen atoms were refined anisotropically for all reflections with I > 2σ(I), and the positions of the hydrogen atoms were generated geometrically and refined by a “riding” model with Uiso(H) = 1.2Ueq(C or O). Table S1 shows the crystallographic data and details of the structure refinements at 293 K and 143 K. CCDC 1841169 (143 K, 1), 1841170 (293 K, 1) contain the supplementary crystallographic data for this paper. These data are provided free of charge by The Cambridge Crystallographic Data Centre. Measurements. Differential scanning calorimetry (DSC) measurements were performed on a PerkinElmer Diamond DSC instrument that samples in aluminum crucibles under a nitrogen atmosphere with heating and cooling rates of 20 K/min from 140 to 260 K. The polycrystalline samples and single crystal of 1 were used to the dielectric measurements. The temperature dependence of complex dielectric constant (ε = ε' - i ε'', where ε' is the real part and the ε'' imaginary part) were carried on a Tonghui TH2828A instrument in the temperature range 143–260 K at frequencies from 5 kHz to 1 MHz with an applied voltage of 1.0 V. The cycles of dielectric switching were also measured on a Tonghui TH2828A instrument in the temperature range 143-260 K and repeated many times over time. Ultraviolet–visible (UV–vis) absorption spectrum. Ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy of 1 (Polycrystalline samples) was measured at room temperature by using a Shimadzu (Tokyo, Japan) UV-2600 spectrophotometer with an ISR-2600Plus integrating sphere in the range of 200-1000 nm. BaSO4 was used as the 100% reflectance reference. The optical bandgap (Eg) of the compound was estimated by converting reflectance data to absorbance according to the Kubelka–

5



Page 6 of 19

Munk equation35: F(R∞)=(1−R∞)2/2R∞. The Eg was determined from the variant of the Tauc equation36: (hν⋅F(R∞))1/n = A(hν - Eg) where h is Planck’s constant, ν is the frequency of vibration, A is proportional constant, F(R∞) is the Kubelka–Munk function, and exponent ‘n’ represents the nature of the sample’s transition, n = 1/2 for direct, and n = 2 for indirect transition. The Eg can be obtained from a Tauc plot by plotting [hν·F(R∞)]1/n against the energy in electron volts. Theoretical calculation. The electronic structures calculations including the electronic band structures and the density of states of 1 were performed based on Density functional theory by using the CASTEP module37, 38 coded in the Materials studio software (Accelrys, San Diego, CA, USA). Construct the theoretical mode by using the crystal structure data at 143 K of 1. The exchange and correlation effects were

used Perdew–Burke–Ernzerhof

to treat in

the

generalized

gradient

approximation. And the core-electrons interactions were described by the norm-conserving pseudopotential. The plane wave cutoff energy and the convergence threshold of total energy were set to 820 eV and 10-5 eV per atom, respectively. The other parameters and convergent criteria were the default values of CASTP code.

RESULTS AND DISCUSSION The crystalline sample of compound 1 was obtained by evaporation of an aqueous solution containing Bismuth Trichloride, Trimethylamine N-oxide dehydrate and hydrochloric acid (36%) (Figure 1a, 1b). To determine the structure of compound 1, we first measured it at 293 K with the X-ray diffraction (XRD). Then in the judgment of the existence of reversible phase transitions by thermal stimuli, we used differential scanning calorimetry (DSC) as an effective method. As depicted in Figure 1c, one pair of peaks in the curves of heating and cooling massed around 183.5 K with a relatively narrow thermal hysteresis about 10.9 K, which indicates that 1 shows a reversible phase transition. And the entropy change ∆S around Tc, which is 8.197 J K-1 mol-1. Based on the Boltzmann equation of ∆S = Rln(N), where R is the gas

6


Page 7 of 19 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


constant, to estimate the number of molecular orientations from the calorimetric data yields N = 2.7 which represents the ratio of the numbers of respective geometrically distinguishable orientations for both phases system, indicating the order-disorder feature of the phase transition.39 For convenience, the phases below and above Tc are labelled as the low-temperature phase (LTP) and the room-temperature phase (RTP), respectively.

Figure 1. (a) The as-grown crystal of compound 1 with the size of 6 × 2 × 1 mm3. (b) The simulative single crystal shape of compound 1. (c) DSC curves of compound 1. For studying the microscopic mechanism of this phase transition and approving the result of DSC measurement, X-ray diffraction analyses of 1 was performed at 143 K to compare with 293 K (Figure 2). At 293 K, it crystallizes in orthorhombic centrosymmetric space group Pnma. Upon cooling to 143 K, the space group of compound 1 changes from Pnma to P212121. For specific SCXRD data of LTP and HTP are arranged in Table S1.

7



Page 8 of 19

Figure 2. Molecular Structural comparison of 1 between the LTP (a) and HTP (b); and the order-disorder transformation of TMNO cation in 1 during this phase transition, the TMNO cation (B) becomes (c) ordered in the LTP and (d) disordered in the HTP. H-atoms are omitted for clarity. With further analysis, we compared the visual structural similarities and differences of the LTP and RTP to understand the phase transition. Figure 2, Figure 3 and Figure S4, S5 are the corresponding displays. Like the previous work, the crystal structures of 1 both in LTP and RTP have a one-dimensional zigzag chains belonging to the BX6-face-sharing hexagonal category of the structure.10,

40, 41

In the LTP, the

molecular structure unit consists of one BiCl2-5 anion and two cations, including TMNO (A) cation and TMNO (B) cation (Figure 2a). Each Bi3+ ion is coordinated by six Cl- ions (four terminal and two bridging Cl- ions) (Table S2) and is linked to other units (the neighboring Bi3+ ion) by the neighboring bridging Cl- ions, and the bond angles of Bi-Cl-Bi are 178.4° (Figure 3a, 3b and S4a). The organic cations are linked to inorganic framework through O−H···Cl hydrogen bonding, showing ordered state (Figure S5a and Table S3). As the temperature goes up over Tc to RTP, the molecular structure unit and coordination geometry of the Bi3+ ion remains the same as LTP and shows little changes (Table S2). But the Bi3+ ion and two terminal Cl- ions are situated on the crystallographic mirror plane which parallels to the c axis and the Bi-Cl-Bi angle is slightly different from LTP, becoming straight-180° (Figure 3c, 3d and S4b). Notably, the organic cations show significant changes. As you see in Figure 2b, the TMNO (A) cations and (B) cations are not only located around the mirror plane, but the (B) cations become disordered (O/O´, C(a)/C(a)´, C(b)/C(b)´) corresponding to the (A) cations remain a relatively static state. The (A) cations and (B) cations by their way to realize symmetry requirement about the mirror plane, of which (A) cations are constructed by symmetry in themselves and (B) cations are achieved through two fold orientational disorder. Besides, only the disordered cations (B) linked to the chain of inorganic by the O2−H2D···Cl3 and O2´−H2D´···Cl3´hydrogen bonding (Figure S5b and Table S4). In short, the primary reason for the phase transition is the dynamic

8


Page 9 of 19 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


motions of organic cations, especially the order-disorder transformation of (B) cations (Figure 2c and 2d). And the movement of cations causes a slight deformation of the inorganic skeleton through hydrogen bonding (Figure 3b and 3d).

Figure 3. Perspective views of the structures of (TMNO)2-BiCl5 at 143 K (LTP) (a) and at 293 K (RTP) (c), showing the similarities in the lattices and the differences of the orientational states of the organic cations. The schematic diagrams of the inorganic framework are shown in (b) LTP and (d) RTP. The Light blue and red dotted lines indicate hydrogen bonding force. As for A and B in Figure 3b show the TMNO cations (the red A and blue A represent organic cations (the same as A in figure 2a) above and below the inorganic linear, respectively; the red B and blue B represent the organic cations (the same as B in the figure 2a) above and below inorganic linear, respectively). As for the B and B´in Figure 3d also show the TMNO cations (the red B and B´ represent organic cations (the same as B in figure 2b) above, the hydrogen bonding atoms are O and O´, respectively; blue B and B´ represent organic cations (the same as B in figure 2b) below the inorganic linear, the hydrogen bonding atoms are O and O´, respectively).

9



Generally, materials with structural phase transitions display a variety of physical properties accompanied by anomalies as responses. In the studying the temperature-dependent dielectric properties of compound 1, anomalies are indeed observed in the reversible cooling/heating cycles, consistent well with thermal anomalies (Figure 4a and S6). As shown in Figure 4a, the temperature dependence of the real parts (ε') remain almost stable above Tc, corresponding to its high-dielectric state. In the cooling process, the dielectric constants reveal the bluff-type changes around Tc, and the values drop from ~18.3 to ~14.4 in the low-dielectric state. Besides, to facilitate the reversibility of the change of its dielectric constant stimulated by temperature, the real parts (ε') and dielectric loss (ε′′) of the polycrystalline sample of 1 were measured at 1000 kHz on cooling and heating are shown in Figure 4b. Step-like anomalies at around Tc were found in cooling and heating processes, respectively. In this regard, these behaviors of dielectric correlate well with its structural phase transition. Furthermore, the prominent anisotropy along the different crystallographic axes was researched on single crystal. The magnitude of the ε' values along a- b- and c-axes at 1000 kHz in the cooling process is different, but the phase transition temperature (Tc) are same (Figure 4c). Obviously, the dielectric anomalies in the direction of c axis are larger than those along b and a axes. This apparent dielectric anisotropy could be ascribed to the motions or reorientations of TMNO cations in frameworks. From LTP to RTP, the thermal vibrations of C and O atoms in the c-axis are more intense, suggesting the dynamic of cations are much more sensitive to the temperature along c axis. In addition, repeated reversible dielectric switches were also performed to prove the stability in the high/low dielectric state conversion. It can be seen in Figure 4d, with the passage of time and a periodic variation of temperature, the intensity of dielectric signals transformed in the high and low state with no decay after manifold cycles. And the dielectric switching cycles and their corresponding temperature profiles over time shown in Figure S7, indicating switching behaviors of 1 were matched closely to the temperature curves. These key

10


Page 10 of 19

Page 11 of 19 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


results show that 1 has some advantages in stability and potential applications in temperature-sensitive devices.

Figure 4. (a) The temperature-dependence of the real part (έ) of the polycrystalline sample of 1 at frequencies from 5 kHz to 1000 kHz upon cooling. (b) The real part of temperature-dependence dielectric constant of 1 on heating and cooling at 1 MHz and inset shows the corresponding dielectric loss. (c) Temperature-dependent dielectric constant (ε′) of 1 measured on crystal samples along a-, b- and c-axes at 1 MHz upon cooling. Inset shows the Schematic diagram of dielectric measurements of 1 along c-axis. (d) Cycles of switching high and low dielectric state of ε' at 100 kHz over time. Hybrid materials based on Sb and Bi are expected to have potential semiconducting properties because of these atoms have the same ionic radii and electro-negativities as the metal atom-Pb.42 As shown in Figure 5a and 5b, UV/Vis reflection spectrum and absorption spectrum of 1 indicate a gradual absorption edge at about 400 nm. The bandgap (Eg) is estimated to be about 3.225 eV by calculating from the Tauc plot (inset of Figure 5b) for 1. The wide bandgap is similar to that of wurtzite GaN (~3.42 eV), which could be used in high power/efficiency optoelectronic devices.43 And the 11



bandgap of 1 can be more easily tuned than GaN. Besides, using the measured imaginary part (ε'') of the complex dielectric permittivity, and the relationship σac = ωε''ε0 (ω is the angular frequency and ε0 is the permittivity of free space)44, the temperature-dependent ac conductivity of compound 1 was studied. The positive slope of ac conductivity with increasing temperature strongly confirms that 1 has the typical feature of semiconductor in the room-temperature phase (Figure S8). Additionally, the temperature-dependent ac conductivity of 1 shows abnormality (turn from rising state to falling state and then return to normal rising state) around phase transition temperature, corresponding to the structural phase transitions (Figure S9). This phenomenon can be attributed to the ordered-disorder transition of polar organic cations, resulting in slight deformation of the inorganic chains, and affecting the ac conductivity of 1 around phase transition temperature. To gain a deeper understanding of the electronic origin of semiconducting properties of 1, the band structure and energy gap were calculated based on density functional theory (DFT). As shown in Figure 5c and S10, the conduction band minimum and the valence band maximum are not localized at the same position in the Brillouin zone indicates that 1 is an indirect bandgap semiconducting material. Meanwhile, the calculated bandgap is 3.562 eV having slightly different from the experimental value 3.225 eV on account of the limitations of the density functional theory method. Furthermore, the result of the bands assigned according to the partial density of states (PDOS) was plotted in Figure 5d. For the organic part, H 1s states overlap fully with C 2s2p, N 2s2p and O 2s2p states in the whole energy region. In the inorganic moieties, not much overlap is observed between Bi 6s/p and Cl 3s/p in the conduction region. Expectantly, there are two peaks near the Fermi level (Ef) of PDOS corresponding to CB minimum and the VB maximum respectively. The VB maximum originates from the nonbonding states of Cl-3p and the CB minimum is mainly from Bi-6p states. Such coupling is produced from the electronic states of the inorganic part (Bi and Cl atoms), revealing that the bandgap of the material is determined by the inorganic BiCl5 framework. 12


Page 12 of 19

Page 13 of 19 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


Figure 5. The diffuse reflectance spectrum (a) and UV-vis absorption spectra (b) of 1. The inset shows the Tauc plot for 1. (c) The calculated energy band structure of 1 (Eg = 3.562 eV). (d) Partial density of states (PDOS) for 1.

CONCLUSIONS In summary, we discovered a one-dimensional semiconducting hybrid switchable dielectric compound (TMNO)2BiCl5 which undergoes a reversible structural phase transition at Tc = 183.5 K. It is found that the order-disorder transformation of polar organic cations and the weak displacements of inorganic frameworks together to make contributions for its switchable dielectric properties. Moreover, the Bi-based inorganic framework determines the semiconducting property with a wider optical bandgap (~3.225 eV). The compound with slightly higher band gap has undoubtedly added new forces to this type of functional hybrid materials because of it can be used in high power/rate optoelectronic devices according to its own nature or tailored towards the potential applications through modifying cations or halide. Namely, the solid-state materials combined with excellent electronic and optical properties are promising in applications on optoelectronic devices.

13



ACKNOWLEDGEMENTS This work was financially supported by the Project 973 (2014CB848800), National Natural Science Foundation of China (21673038, 21771037), and Program for SEU.

ASSOCIATED CONTENT Supporting Information Available: (Supporting information includes Supplementary Text, Figures S1 to S10 and Tables S1 to S4. Infrared spectra, XRD powder pattern, TGA curve, the differences of the crystal structures and hydrogen bonding interactions between anions and cations about low temperature phase and room temperature phase, dielectric spectra of 1 at various frequencies in the heating mode, the recoverable switching of dielectric effects with temperature, the conductivity behaviors of 1, and the calculated energy band structure of 1 (Figures S1-S10, respectively). Tables S1-S4: crystal data and structural refinement details for compound 1 at temperatures of 143 and 293 K, the selected bond lengths and angles, and hydrogen-bond data for 1 at the temperature of 143 and 293 K.) This material is available free of charge via the internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Authors E-mail: [email protected]. E-mail: [email protected]. Notes The authors declare no competing financial interest.

REFERENCES (1) Li, W.; Wang, Z. M.; Deschler, F.; Gao, S.; Friend, R. H.; Cheetham, A. K. Chemically Diverse and Multifunctional Hybrid Organic-Inorganic Perovskites. Nat. Rev. Mater., 2017, 2, 16099. (2) 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. (3) Liao, W. Q.; Zhao, D. W.; Yu, Y.; Grice, C. R.; Wang, C.; Cimaroli, A. J.; Schulz, P.; Meng, W.; Zhu, K.; Xiong, R. G.; et al. Lead-Free Inverted Planar

14


Page 14 of 19

Page 15 of 19 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


Formamidinium Tin Triiodide Perovskite Solar Cells Achieving Power Conversion Efficiencies Up to 6.22. Adv. Mater., 2016, 28, 9333-9340. (4) Yuan, Z.; Zhou, C. K.; Tian, Y.; Shu, Y.; Messier, J.; Wang, J. C.; van de Burgt, L. J.; Kountouriotis, K.; Xin, Y.; Holt, E.; et al. One-Dimensional Organic Lead Halide Perovskites with Efficient Bluish White-Light Emission. Nat. Commun., 2017, 8, 14051. (5) Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J.; Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber. Science, 2013, 342, 341-344. (6) Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith, H. J. Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites. Science, 2012, 1228604. (7) Kazim, S.; Nazeeruddin, M. K.; Gratzel, M.; Ahmad, S. Perovskite as Light Harvester: a Game Changer in Photovoltaics. Angew. Chem., Int. Ed., 2014, 53, 2812-2824. (8) Ponseca, C. S., Jr.; Savenije, T. J.; Abdellah, M.; Zheng, K.; Yartsev, A.; Pascher, T.; Harlang, T.; Chabera, P.; Pullerits, T.; Stepanov, A.; et al. Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination. J. Am. Chem. Soc., 2014, 136, 5189-5192. (9) Li, P.-F.; Tang, Y.-Y.; Liao, W.-Q.; Ye, H.-Y.; Zhang, Y.; Fu, D.-W.; You, Y.-M.; Xiong, R.-G. A Semiconducting Molecular Ferroelectric with a Bandgap Much Lower than That of BiFeO3. NPG Asia Mater., 2017, 9, e342-e342. (10) Mercier, N.; Louvain, N.; Bi, W. Structural Diversity and Retro-Crystal Engineering Analysis of Iodometalate Hybrids. CrystEngComm, 2009, 11, 720-734. (11) Ye, H. Y.; Liao, W. Q.; Hu, C. L.; Zhang, Y.; You, Y. M.; Mao, J. G.; Li, P. F.; Xiong, R. G. Bandgap Engineering of Lead-Halide Perovskite-Type Ferroelectrics. Adv. Mater., 2016, 28, 2579-2586. (12) Stroppa, A.; Di Sante, D.; Barone, P.; Bokdam, M.; Kresse, G.; Franchini, C.; Whangbo, M. H.; Picozzi, S. Tunable Ferroelectric Polarization and Its Interplay with Spin-Orbit Coupling in Tin Iodide Perovskites. Nat. Commun., 2014, 5, 5900. (13) Sun, Z. H.; Zeb, A.; Liu, S. J.; Ji, C. M.; Khan, T.; Li, L.; Hong, M. C.; Luo, J. H. Exploring a Lead-Free Semiconducting Hybrid Ferroelectric with a Zero-Dimensional Perovskite-like Structure. Angew. Chem., Int. Ed., 2016, 55, 11854-11858. (14) Wang, S. S.; Li, L.; Sun, Z. H.; Ji, C. M.; Liu, S. J.; Wu, Z. Y.; Zhao, S. G.; Zeb, A.; Hong, M. C.; Luo, J. H., A Semi-Conductive Organic–Inorganic Hybrid Emits Pure White Light With an Ultrahigh Color Rendering Index. J. Mater. Chem. C, 2017, 5, 4731-4735.

15



(15) Mączka, M.; Ciupa, A.; Gągor, A.; Sieradzki, A.; Pikul, A.; Ptak, M. Structural, Magnetic and Dielectric Properties of Two Novel Mixed-Valence Iron(ii)–Iron(iii) Metal Formate Frameworks. J. Mater. Chem. C, 2016, 4, 1186-1193. (16) Xu, W. J.; He, C. T.; Ji, C. M.; Chen, S. L.; Huang, R. K.; Lin, R. B.; Xue, W.; Luo, J. H.; Zhang, W. X.; Chen, X. M. Molecular Dynamics of Flexible Polar Cations in a Variable Confined Space: Toward Exceptional Two-Step Nonlinear Optical Switches. Adv. Mater., 2016, 28, 5886-5890. (17) Sato, O.; Tao, J.; Zhang, Y. Z. Control of Magnetic Properties Through External Stimuli. Angew. Chem., Int. Ed., 2007, 46, 2152-2187. (18) Manson, J. L.; Kmety, C. R.; Huang, Q. Z.; Lynn, J. W.; Bendele, G. M.; Pagola, S.; Stephens, P. W.; Liable-Sands, L. M.; Rheingold, A. L.; Epstein, A. J. Charge Ordering and Related Properties of Manganese Oxides Ed CNR Rao and B Raveau. Chem. Mater., 1998, 10, 2552-2560. (19) Shao, X. D.; Zhang, X.; Shi, C.; Yao, Y. F.; Zhang, W. Switching Dielectric Constant Near Room Temperature in a Molecular Crystal. Adv. Sci (Weinh), 2015, 2, 1500029. (20) Wang, S. S.; Chen, X. X.; Huang, B.; Su, Y. J.; Zhang, W. X.; Zeng, M. H.; Chen, X. M. Bromocholine Bromide is a Molecular Ferroelectric with Moderate Phase Transition Temperature. J. Mater. Chem. C, 2018, 6, 2221-2224. (21) Liao, W. Q.; Tang, Y. Y.; Li, P. F.; You, Y. M.; Xiong, R. G. Competitive Halogen Bond in the Molecular Ferroelectric with Large Piezoelectric Response. J. Am. Chem. Soc., 2018, 140, 3975-3980. (22) Kawata, S.; Kawata, Y. Three-Dimensional Optical Data Storage Using Photochromic Materials. Chem. Rev., 2000, 100, 1777-1788. (23) Shen, J.; Cong, J.; Chai, Y.; Shang, D.; Shen, S.; Zhai, K.; Tian, Y.; Sun, Y. Nonvolatile Memory Based on Nonlinear Magnetoelectric Effects. Phys. Rev. Applied., 2016, 6, 021001. (24) Feringa, B. L.; van Delden, R. A.; Koumura, N.; Geertsema, E. M. Chiroptical Molecular Switches. Chem. Rev., 2000, 100, 1789-1816. (25) 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. (26) Shi, P. P.; Tang, Y. Y.; Li, P. F.; Liao, W. Q.; Wang, Z. X.; Ye, Q.; Xiong, R. G. Symmetry Breaking in Molecular Ferroelectrics. Chem. Soc. Rev., 2016, 45, 3811-3827. (27) Xu, W. J.; Du, Z. Y.; Zhang, W. X.; Chen, X. M. Structural Phase Transitions in Perovskite Compounds Based on Diatomic or Multiatomic Bridges. CrystEngComm, 2016, 18, 7915-7928. (28) Zeb, A.; Sun, Z. H.; Khan, A.; Zhang, S. Q.; Khan, T.; Asghar, M. A.; Luo, J. H. [C6H14N]PbI3: a One-Dimensional Perovskite-like Order–Disorder Phase Transition Material with Semiconducting and Switchable Dielectric Attributes. Inorg. Chem. Front., 2018, 5, 897-902. (29) Saparov, B.; Mitzi, D. B. Organic-Inorganic Perovskites: Structural Versatility for Functional Materials Design. Chem. Rev., 2016, 116, 4558-4596. 16


Page 16 of 19

Page 17 of 19 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


(30) Gagor, A.; Banach, G.; Weclawik, M.; Piecha-Bisiorek, A.; Jakubas, R. The Lone-Pair-Electron-Driven Phase Transition and Order-Disorder Processes in Thermochromic (2-MIm)SbI4 Organic-Inorganic Hybrid. Dalton Trans., 2017, 46, 16605-16614. (31) Zeb, A.; Sun, Z. H.; Khan, T.; Asghar, M. A.; Wu, Z. Y.; Li, L.; Ji, C. M.; Luo, J. H. [C5H12N]CdCl3: an ABX3 Perovskite-Type Semiconducting Switchable Dielectric Phase Transition Material. Inorg. Chem. Front., 2017, 4, 1485-1492. (32) Li, L.; Shang, X. Y.; Wang, S. S.; Dong, N. N.; Ji, C. M.; Chen, X. Y.; Zhao, S. G.; Wang, J.; Sun, Z. H.; Hong, M. C.; et al. Bilayered Hybrid Perovskite Ferroelectric with Giant Two-Photon Absorption. J. Am. Chem. Soc., 2018, 140, 6806-6809. (33) Wu, Z. Y.; J, C. M.; Li, L.; Kong, J. T.; Sun, Z. H.; Zhao, S. G.; Wang, S. S.; Hong, M. C.; Luo, J. H. Alloying n-Butylamine into CsPbBr3 To Give a Two-Dimensional Bilayered Perovskite Ferroelectric Material. Angew. Chem. Int. Ed., 2018, 57, 8140-8143. (34) Zhang, H. Y.; Wei, Z.; Li, P. F.; Tang, Y. Y.; Liao, W. Q.; Ye, H. Y.; Cai, H.; Xiong, R. G. The Narrowest Band Gap Ever Observed in Molecular Ferroelectrics: Hexane-1,6-Diammonium Pentaiodobismuth(III). Angew. Chem. Int. Ed., 2018, 57, 526-530. (35) Kortüm, G.; Braun, W.; Herzog, G. Principles and Techniques of Diffuse‐ Reflectance Spectroscopy. Angew. Chem. Int. Ed., 1963, 75, 653-661. (36) Tauc, J.; Grigorovici, R.; Vancu, A. Optical Properties and Electronic Structure of Amorphous Germanium. Phys. Status. Solidi. B, 1966, 15, 627-637. (37) Terki, R.; Bertrand, G.; Aourag, H. Full Potential Investigations of Structural and Electronic Properties of ZrSiO4. Microelectron. Eng., 2005, 81, 514-523. (38) Godby, R. W.; Schlüter, M.; Sham, L. J. Trends in Self-Energy Operators and Their Corresponding Exchange-Correlation Potentials. Phys. Rev. B, 1987, 36, 6497-6500. (39) Zhang, W.; Ye, H. Y.; Graf, R.; Spiess, H. W.; Yao, Y. F.; Zhu, R. Q.; Xiong, R. G. Tunable and Switchable Dielectric Constant in an Amphidynamic Crystal. J. Am. Chem. Soc., 2013, 135, 5230-5233. (40) Xu, G.; Li, Y.; Zhou, W. W.; Wang, G. J.; Long, X. F.; Cai, L. Z.; Wang, M. S.; Guo, G. C.; Huang, J. S.; Bator, G.; et al. A Ferroelectric Inorganic–Organic Hybrid Based on NLO-Phore Stilbazolium. J. Mater. Chem., 2009, 19, 2179-2183. (41) Wang, Y.; Shi, C.; Han, X. B. Mixed Bromine–Chlorine Induced Great Dielectric and Second-Order Nonlinear Optical Properties Changes in Phase Transitions Compounds [H2mdap][BiBr5(1-x)Cl5x] (x = 0.00–1.00). J. Phys. Chem. C, 2017, 121, 23039-23044. (42) Shannon, R. D. Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides. Acta Crystallogr. Sect. A 1976, 32, 751-767.

17



(43) Simon, J.; Zhang, Z.; Goodman, K.; Xing, H.; Kosel, T.; Fay, P.; Jena, D. Polarization-Induced Zener Tunnel Junctions in Wide-Band-Gap Heterostructures. Phys. Rev. Lett., 2009, 103, 026801. (44) Kuang, W.; Nelson, S. O. Low-Frequency Dielectric Properties of Biological Tissues: a Review with Some New Insights. Transactions of the ASAE, 1998, 41, 173-184.

18


Page 18 of 19

Page 19 of 19 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


TOC Graphic:

19


Semiconducting OrganicâInorganic Hybrid Material with Distinct

Recommend Documents

Semiconducting OrganicâInorganic Hybrid Material with Distinct