OrganicâInorganic Hybrid Heterometallic Halides with Low

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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Organic−Inorganic Hybrid Heterometallic Halides with LowDimensional Structures and Red Photoluminescence Emissions Cheng-Yang Yue,†,# Chen Sun,†,‡,# Dong-Yang Li,† Yu-Han Dong,† Chun-Lei Wang,† Hui-Fang Zhao,† Hao Jiang,† Zhi-Hong Jing,*,‡ and Xiao-Wu Lei*,† †

Department of Chemistry and Chemical Engineering, Jining University, Qufu, Shandong 273155, P. R. China College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, Shandong 273165, P. R. China

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S Supporting Information *

ABSTRACT: In recent years, although low-dimensional hybrid lead halides have received great attention due to the fascinating photoluminescent (PL) properties, the research is still on the early stage and only limited phases have been explored and characterized. Here, by introducing heterometals as mixed structural compositions and optical activity centers, we prepared a series of lowdimensional hybrid heterometallic halides, namely as, [(Me)-DABCO]2Cu2PbI6, [(Me)2-DABCO]2M5Pb2I13 (M = Cu and Ag) and [(Me)2DABCO]Ag2PbBr6 (Me = methyl group, DABCO = 1,4-diazabicyclo[2.2.2]octane). These hybrid halides feature a low-dimensional 0D [Cu2PbI6]2− cluster, a 1D [M5Pb2I13]4− chain, and a 2D [Ag2PbBr6]2− layer, respectively, on the basis of corner-, edge- and face-sharing connecting of [MX4] tetrahedrons, [PbX5] quadrangular pyramids, and [PbX6] octahedrons. Under the photoexcitation, these hybrid heterometallic halides exhibit deep-red luminescent emissions from 711 to 801 nm with the largest Stocks shift of 395 nm. The temperature-dependent PL emissions, PL lifetime, and theoretical calculations are also investigated to probe into the intrinsic nature of photoluminescent emissions. This work affords new types of hybrid halides by introducing different metal centers to probe into the structural evolution and photoluminescent properties.

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INTRODUCTION

PL properties of low-dimensional hybrid halide perovskites based on the structural analysis. As well-known, low-dimensional hybrid lead halides belong to one type of unique system with tunable photoluminescent properties derived from the synergistic contributions of organic and inorganic constituents. On the one hand, the spatial stereoscopic effects of organic cations play the critical roles in modifying the anionic structural types and distortion degrees of [PbX6] units, which dynamically regulate the band structures and optoelectronic properties of hybrid perovskites.12 Furthermore, some hybrid metal halides are also able to directly exhibit the characteristic emissions mainly originating from the organic cations.13 On the other hand, the inorganic skeletons make the direct contribution to the band structures and play a very important function in determining the excited state energy and PL properties. Hence, the diversified organic cations and variegated inorganic halide skeletons afford multiple design strategies to regulate the PL properties of hybrid lead halides. In recent years, substantial research work concentrates on the structural and property regulations by changing the organic cations, but rare attention is contributed to directly regulating the structural types of inorganic skeletons by enriching the constructing

Hybrid metal halides have been widely investigated in recent years with the advantages of abundant structural types, adjustable band structures, and extensive application values in various optoelectronic fields.1−6 Among all the hybrid halides, the perovskite lead halides feature rich structural modifiabilities of three-dimensional (3D) frameworks, twodimensional (2D) layers, and one-dimensional (1D) chains by varying the chemical components. In particular, the lowdimensional hybrid perovskites exhibit excellent luminescent emissions derived from the free and/or self-trapped excited states due to strong quantum confinement effects.7−9 It is reported that a series of low-dimensional hybrid lead halides exhibiting broadband white-light emissions have been explored, such as C5H14N2PbCl4 (1D), C4N2H14PbBr4 (1D), (EDBE)[PbX 4 ] (2D, EDBE = 2,2′-(ethylenedioxy)bis(ethylammonium)), α-(DMEN)PbBr4 (2D, DMEN = 2(dimethylamino)ethylamine), (N-MEDA)[PbBr4] (2D, NMEDA = N-methylethane-1,2-diammonium), and (2MeptH2)PbBr4 (2D, 2Mept = 2-methyl-1,5-diaminopentane), etc.10,11 Furthermore, the photophysical properties of low-dimensional halides show highly structural adjustabilities by engineering the chemical composition and dimensionality as well as the structural distortion degrees. Hence, it is remain important and challenging to understand this material and improve the © XXXX American Chemical Society

Received: May 20, 2019

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DOI: 10.1021/acs.inorgchem.9b01472 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

sealed in a 15 mL stainless steel reactor. The reactor was first heated at 140 °C for 5 days and then slowly cooled to room temperature with a cooling rate of 5 °C·min−1. After the filtration, block-shaped orange crystals were obtained and subsequently determined as [(Me)-DABCO]2Cu2PbI6 (1). After crystal structural determination, crystals of compound 1 were collected under a microscope in 15% yield based on PbI2 and then washed, dried, and preserved in a vacuum. Anal. Calcd for C14N4H30Cu2PbI6 (1): C, 12.45; N, 4.15; H, 2.24. Found: C, 12.59; N, 4.25; H, 2.12. IR (cm−1): 3429 (m), 3028 (m), 2373 (w), 1633 (s), 1467 (s), 1284 (s), 1182 (m), 829 (m), and 492 (m). Syntheses of Compounds [(Me)2-DABCO]2Cu5Pb2I13 (2) and [(Me)2-DABCO]2Ag5Pb2I13 (3). Yellow crystals of compound 2 were obtained by solvothermal reaction of CuI (1 mmol), PbI2 (0.5 mmol), and KI (3 mmol) in a mixed solution of methanol (3 mL) and hydriodic acid (4 mL, 47%) at 140 °C for 5 days. After filtration, yellow crystals were collected with yield of 48% based on PbI2 and purity was verified by PXRD. Anal. Calcd for C16N4H36Cu5Pb2I13: C, 7.21; H, 1.36; N, 2.10%. Found: C, 7.29; H, 1.21; N, 2.20%. IR (cm−1): 3437 (s), 2982 (w), 2378 (w), 1646 (m), 1454 (s), 1132 (w), 1062 (w) and 830 (m). Yellow block-shaped crystals of compound 3 were prepared via the same reaction condition with AgI as a substitute for CuI in yield of 21% based on PbI2. Anal. Calcd for C16N4H36Ag5Pb2I13 (3): C, 6.65; H, 1.26; N, 1.94. Found: C, 6.79; H, 1.35; N, 2.11. IR (cm−1): 3434 (s), 2991 (w), 2373 (w), 1633 (s), 1454 (m), 1135 (w), and 833 (w). Synthesis of Compound [(Me)2-DABCO]Ag2PbBr6 (4). A mixture of AgBr (1 mmol), PbBr2 (0.5 mmol), and KBr (2 mmol) was dissolved in a mixed solution in methanol (2 mL) and hydrobromic acid (5 mL, 48%), and the suspension was sealed in a 15 mL stainless steel reactor. After reaction at 140 °C for 5 days, yellow block-shaped crystals were prepared and determined as [(Me)2-DABCO]Ag2PbBr6 by using X-ray single crystal diffraction. The crystals were filtered off, washed with methanol and stored under vacuum (32% yield based on PbBr2). Anal. Calcd for C8N2H18Ag2PbBr6: C, 9.20; H, 1.74; N, 2.68. Found: C, 9.29; H, 1.63; N, 2.60. IR (cm−1): 3434 (m), 3008 (m), 2370 (w), 1646 (m), 1459 (s), 1140 (m), 1058 (m) and 838 (s). X-ray Crystallography. All the single crystal data of title compounds were collected on the Bruker Apex II CCD diffractometer with Mo Kα radiation (λ = 0.71073 Å) at room temperature. The crystal structures were solved by direct method and refined based on F2 using SHELXTL-97 program.18 All the non-hydrogen atoms were refined with anisotropic thermal parameters, and hydrogen atoms of organic molecules were positioned geometrically and refined isotropically. Structural refinement parameters of compounds 1−4 are summarized in Tables S1 and S2, and important bond lengths are listed in Tables S3−S13. Calculation Details. Single-crystal structural data of the title compounds were directly used for the theoretical calculations. The density of states for title compounds are calculated by with the total-energy code CASTEP.39 The total energy was calculated with density functional theory (DFT) using Perdew−Burke−Ernzerhof (PBE) generalized gradient approximation.19 The interactions between the ionic cores and the electrons were described by the norm-conserving pseudopotential.19 Hence, the C-2s22p2, N-2s22p3, H-1s1, Cu3d104s1, Ag-4d105s1, Pb-6s26p2, Br-4s24p5, and I-5s25p5 was adopted as valence electrons. The numbers of plane waves

building units.14 Compared with the hybrid lead halides, the hybrid heterometallic halides containing two different types of metal centers in inorganic skeletons are able to exhibit more structural adjustabilities, affording another design strategy to regulate not only the inorganic topologies but also electronic band structures.15 Well-known, d10 transition metal (TM) halides are in principle very promising candidates of luminescent materials possessing various advantages including diversified structural topologies, excited multiplet states, adjustable emission wavelengths, high PL quantum yields, inexpensive recourse, nontoxicities, and so on.16 Compared with hybrid lead halides, the d10 TM halides feature more multifarious coordination configurations of linear MX2, triangle MX3, and tetrahedral MX4 units (M = Cu, Ag, X = I, Br) as well as diversified interconnecting modes including face-, edge- and cornersharing. Furthermore, the abundant weak cuprophilicities (Cu···Cu) and argentophilicities (Ag···Ag) also enable new tunable strategies to modify the optoelectronic properties, which have been observed in substantial cuprous and sliver complexes.17 Considering the diversified coordination geometries and tunable photophysical properties of hybrid d10 TM and lead halides, we adopt the strategy of introducing the d10 TM of CuI or AgI into hybrid lead halides, which incorporate the TM-X and Pb-X bonding in hybrid heterometallic halides with more flexible structural building units and organization manners. Moreover, the d10 TMs are also able to decorate the band structures and further induce new optical performance of hybrid heterometallic halides. Compared with substantial hybrid single metal halides, limited hybrid heterometallic halides have been explored and structurally characterized up to the present.15 Here, by using the same N-methylation DABCO as organic cations, we prepared a series of new hybrid heterometallic halides, namely, [(Me)-DABCO]2Cu2PbI6 (1), [(Me)2-DABCO]2M5Pb2I13 (M = Cu (2) and Ag (3)), and [(Me)2-DABCO]Ag2PbBr6 (4). Under the excitation of UV or violet light, these hybrid heterometallic halides exhibit broad red emissions from 711 to 801 nm with the largest Stocks shift of 395 nm. This work affords a new design strategy to prepare red to near-infrared PL materials.

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EXPERIMENT Materials and Instruments. All the chemical reagents in the experimental process were commercially purchased and directly used without further purification. Powder X-ray diffraction (PXRD) data was collected on Bruker D8 Advance diffractometer (Cu Kα, λ = 1.5418 Å) in the 2θ range 5−80°. Elemental analyses for C, N, and H atoms were performed on a Vario Macro elemental analyzer. The solid state UV−vis absorption optical spectra for powder sample were collected at PE Lambda 900 UV/vis spectrophotometer at room temperature in wavelength range of 200−800 nm. The thermogravimetric analysis (TGA) was carried out on a Mettler TGA/ SDTA 851 thermal analyzer from room temperature to 800 °C under the flow of nitrogen atmosphere. The solid state photoluminescence spectrum was recorded on Edinburgh Instruments Analyzer Model FL920 with an excitation source of a 450 W xenon lamp. Synthesis of Compound [(Me)-DABCO]2Cu2PbI6 (1). PbI2 (0.05 mmol), CuI (1 mmol) and KI (3 mmol) were dissolved in mixed solution in methanol (3 mL), hydriodic acid (1 mL, 47%), and DMF (3 mL), and the mixture was then B


Article

Inorganic Chemistry included in the basis sets were determined by a cutoff energy of 320, 290, 300, and 330 eV for compounds 1−4, respectively. The numerical integration of the Brillouin zone is performed using Monkhorst−Pack k-point sampling of 2 × 2 × 2, 2 × 2 × 2, 2 × 2 × 2, and 3 × 2 × 2 for compounds 1−4, respectively. Other calculating parameters and convergence criteria were set by the default values of the CASTEP code.

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RESULTS AND DISCUSSION Compounds 1−4 were solvothermally prepared by using the starting materials of metal halides, DABCO, HI (HBr), and MeOH in organic solvent (Scheme 1). In the solvothermal Scheme 1. Diagram of Reaction Process for Compounds 1− 4

reaction, the methanol molecules (CH3OH) are first activated by HI or HBr under acidic conditions to form CH3I or CH3Br, which further react with the organic amine of DABCO to form N-alkylated [(Me)-DABCO]+ and [(Me)2-DABCO]2+ cations in a nucleophilic substitution reaction. Such in situ reaction of organic cation has been found in other organic cation directed hybrid compounds.3 Structural Description. The structure of compound 1 crystallizes in the cubic space group Pa3̅ and contains a isolated electroneutral [(Me)-DABCO]2Cu2PbI6 unit. In compound 1, the Cu+ ion is coordinated by three iodine and one nitrogen atom from [(Me)-DABCO]+ cation in a tetrahedral coordination environment. Two opposite [(Me)DABCO]CuI3 units are bridged by one [PbI6] octahedron via face-sharing to form an electroneutral [(Me)-DABCO]2Cu2PbI6 (Figure 1). Such connection simultaneously leads to weak Cu···Pb bonds of 2.802(5) Å, which have not been reported in other hybrid cuprous lead halides, such as [PbCu6I8](PPh3)6] (PPh3 = triphenylphosphine), (Bu4N)(PbCuI4) (Bu4N = tetrabutylamine), [Co(phen)3]2[Pb3Cu6I16]·C2H5OH, etc.20 All the [(Me)-DABCO]2Cu2PbI6 units feature parallel stacking along three crystallographic axes (Figure 2a). Compounds 2 and 3 belong to isomorphic phases and contain 1D [Cu5Pb2I13]4− and [Ag5Pb2I13]4− chains separated by [(Me)2-DABCO]2+ cations, respectively. We take compound 2 as represent to depict their crystal structures. In compound 2, three Cu+ ions are tetrahedrally coordinated by four iodine atoms and the Cu−I bond distances of 2.6401(15)−2.7461(16) Å are comparable with those of hybrid phases, such as [H2 dpp][Cu2I4] (dpp = 1,3-di(4pyridyl)-propane), [H2 dpp]2Cu11I15 and [TM(2,2-bipy)3]Cu5I7, etc.21 One Cu(2)I4, two Cu(1)I4, and two Cu(3)I4 tetrahedral units are interlinked via coplanar manner to form a [Cu5I11] secondary building unit (SBU) along with weak cuprophilicity bonds (Cu···Cu) of 2.7539(19) and 3.046(2) Å, which are close to the sum of van der Waals radii of two Cu

Figure 1. Detailed structures of [(Me)-DABCO]2Cu2PbI6 unit in compound 1 (a), 1D [Cu5Pb2I13]4− chain in compound 2 (b), and the 2D [Ag2PbBr6]2− layer in compound 4 (c).

Figure 2. Stacking structural diagrams of compounds 1, 2, and 3. Green and red polyhedrons represent the tetrahedral units around Cu/Ag and octahedral or tetragonal pyramidal units around Pb atoms, respectively.

atoms (2.80 Å).22 Neighboring [Cu5I11] SBUs feature reversed packing manner, which are further bridged by [PbI5] tetragonal pyramids by sharing common edges to form the 1D [Cu5Pb2I13]4− chain (Figure 1b). [(Me)2-DABCO]2+ C


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Inorganic Chemistry cations locate among the parallel [Cu5Pb2I13]4− chains and connect them with weak hydrogen C−H···I bonds (Figure 2b). The structure of compound 4 contains 2D [AgPb2Br6]2− layers separated by [(Me)2-DABCO]2+ cations. In the structural unit of compound 4, two Pb and four Ag atoms adopt octahedral and tetrahedral coordination environments, respectively. Four independent AgBr4 tetrahedrons successively connect via sharing corner I atoms into 1D curving Ag4Br12 chain down the b-axis. Along the c-axis, the neighboring Ag4Br12 chains feature parallel alignment, which are linked by the Pb(1) and Pb(2) atoms via Pb−Br bonds to form the 2D [AgPb2Br6]2− layers containing one type of 10-membered [Pb2Ag3Br5] ring (Figure 1c). The parallel 2D [AgPb2Br6]2− layers are separated and connected by the [(Me)2-DABCO]2+ cations with weak C−H···Br bonds into a 3D super molecular network (Figure 2c). All the Ag−Br bond lengths are in the range 2.6006(17)−3.022(2) Å, which are comparable with those of [Ag6Br11]5− and [Ag13Br17]4− layers, etc.23 The Pb−Br bond lengths (2.8730(12)−3.2233(13) Å) are close to those of (2meptH2)PbBr4, [B(HIm)4]4Pb13Br38 (B(HIm)4 = tetrakis(imidazolyl)borate), (H4TIMM)Pb7Br18 (TIMM = tetrakis(Nimidazolemethylene)methane), etc.13b,24 For all we know, [(Me)2-DABCO]Ag2PbBr6 belongs to the first hybrid Ag− Pb−Br phase directed by organic cations. Thermal Stabilities and Optical Properties. For all the title compounds, we test the thermal stabilities by using thermogravimetric analysis method from room temperature to 800 °C (Figure S4). The results show that compounds 1−4 keep stable until to about 250 °C, and feature approximate two-step decomposition until 800 °C. Solid state UV−vis optical absorption spectra were performed on ground crystal samples of 1−4, and the optical band gaps are estimated as 2.35, 2.34, 2.33, and 2.77 eV by extrapolating the linear portion of the absorption edges, respectively. The band gaps of hybrid heterometallic halides feature obviously red shift comparing with those of aliphatic organic cations directed lead or cuprous iodides and bromides, such as (Me2DABCO)2(PbI6) (3.23 eV), (Et 2 DABCO) 2 (Pb 3 I 10 ) (2.77 eV, Et = ethyl group), (Pr2DABCO)2(Pb3I10) (2.70 eV, Pr = propyl group), H(H3O)(H2DABCO)(PbI6) (2.94 eV) and (Me 2 DABCO) 3 (H 2 DABCO) 2 (Pb 7 I 24 ) (2.62 eV) and (H4TIMM)Pb7Br18 (3.1 eV), etc.24b,25 To get an insight into the optical absorption essence, theoretical studies for compounds 1-4 were carried out based on the CASTEP code. The calculated band gaps of 1.99, 2.08, 2.19, and 2.34 eV, respectively, are slightly smaller than the experimental values obtained from the UV−vis absorption spectra because the DFT method maybe underestimates the band gaps of some insulators and semiconductors (Figure S6). In the total density of states and partial density of states, the aliphatic organic cations in 1−4 make negligible contribution to the orbital near the Fermi level, which suggest that they only indirectly influence the band structure via modulating the structures of the anionic skeletons. The top of occupied molecular orbital are composed of the mixed Cu-3d or Ag-4d and I-5p or Br-4p with minor Pb-6p orbital electrons, and the bottom of unoccupied molecular orbital are mainly derived from the hybrid orbital of Pb-6p and I-5s5p or Br-4s4p. Hence, the optical absorption of title compounds (Figure 3) can be considered as the charge transfer from the Cu/Ag−Br/I banding to Pb−I/Br states in the anionic heterometallic networks.

Figure 3. Solid state UV−vis absorption spectra of compounds 1−4.

Luminescent Properties. Considering the interesting optoelectronic perform of hybrid metal halogenides, we further investigated the luminescent properties of the title compounds and the PL spectra at room temperature are listed in Figure 4a and Table 1. Under UV light (362 nm) excitation, compound 1 gives a red luminescent emission band centered at 727 nm with full-width at half-maximum (fwhm) of 188 nm and Stocks shift of 365 nm. Under the excitation of violet light (406 nm), compound 2 exhibits red luminescent emission with maximum peak, fwhm, and Stocks shift of 753, 215, and 347 nm, respectively. Compared with compound 2, the excitation (422 nm) and emission spectra (801) of the isostructural compound 3 shows slightly red shifts with larger fwhm of 247 nm and Stocks shift of 379 nm, which is comparable with the smaller band gap. Furthermore, compound 3 also give a weak shoulder emission peak in NIR region at about 1044 nm. Excited by 316 nm UV light, compound 4 also generated red light emission centered at 711 nm and exhibited a large fwhm of 239 and Stocks shift of 395 nm. The corresponding Commission Internationale de l’Eclairage (CIE) color coordinates (x, y) are (0.67, 0.32), (0.67, 0.33), (0.71, 0.29) and (0.60, 0.39) for compounds 1−4, respectively, which are close to that of pure red light (0.68, 0.32). The time-resolved PL decay profiles of the title compounds at room-temperature are given in Figure S7. All the PL decay profiles monitoring the intensity at maximum emission wavelength are fitted by double exponential functions with average lifetime of 0.20, 0.04, 0.19, and 0.05 μs, respectively. The short lifetimes of the emitting peaks of compounds 1−4 indicate their fluorescence nature. The luminescent emissions of these hybrid heterometallic halides are close to those of (PPh3)4Cu2PbI4 (732 nm) and (PPh3)6[PbCu6I8] (λmax = 785 nm) with 0D isolated molecular structures.20 However, they feature obvious red shifts comparing with some lead complexes decorated iodoargentates, such as [Pb(tepa)]Ag 2 I 4 (518 nm), [Pb(dien)3(CO3)]6Ag8I15 (539 and 582 nm) and [PbI2(DMF)2][PbAg2(PPh3)2I4] (566 nm), etc.26 Compared with most of the hybrid single metal halides, all the title heterometallic halides contain two different types of metal centers and possess larger Stocks shifts from 347 to 395 nm, such as (C9NH20)2SnBr4 (332 nm, C9NH20 = 1-butyl-1-methylpyrrolidinium), C4N2H14PbCl4 (244 nm, C4N2H14 = N,N′-dimethylethylene-1,2-diammonium), (C4N2H14Br)4SnBr6 (215 nm), (Ph4P)2SbCl5 (273 nm, Ph4P = tetraphenylphosphonium), D


Article

Inorganic Chemistry

Figure 4. Excitation and emission spectra of compounds 1−4.

actions between electron and phonon in the distorted inorganic skeleton. Such a phenomenon has been identified in many hybrid low-dimensional perovskites.28 In addition, the quenching of emission intensities is also associated with the reduced nonradiation process of thermal vibration with temperature decreasing. As a result, the relationship of PL emission intensity and 1/T can be fitted by using the Arrhenius formula:

Table 1. Summary of Photophysical Properties for Compounds 1−4a materials λabs [nm] λex [nm]

λem [nm]

Stocks shift [nm]

fwhm [nm]

527 529 532 447

727 753 801 711

365 347 379 395

188 215 247 239

1 2 3 4

362 406 422 316

λabs, λex, and λem represent the wavelength of absorbance edge, excitation, and maxima emission, respectively.

a

IPL =

I0

( )

1 + a exp

−Ea kBT

Here IPL is the emission intensity at different temperature (T), I0 is the emission intensity at 80 K, Ea belongs to the activation energy related to the thermally activated nonradiation process, and KB represents the Boltzmann constant. As shown in Figure S8, the theoretical fitted activation energy Ea of 71.8−80.3 meV are close to those of RZnBr3, R2CdBr4, and RCdI3 (R = [C6(CH3)5CH2N(CH3)3]), etc.13 To better understand the PL origins of our hybrid halides, the emissions of precursor organic molecule [(Me)2-DABCO]X2, bulk AgX, CuX, and PbX2 (X = Br, I) were also investigated as reference (Figure S9). Under the UV excitation, both [(Me)2-DABCO]X2 moieties display weak blue light emissions centered at about 415−428 nm, and CuI, AgI, and AgBr show weak red light emissions with maximum peaks of about 735, 723, and 700 nm, respectively. Bulk PbI2 and PbBr2 exhibit

C4N2H14PbBr4 (115 nm), (2meptH2)PbClxBr4‑x (222 nm), etc.10b,12,27 Our work affords an effective method to design new types of IR or NIR luminescent halide materials with large Stocks shifts and potential applications in biological imaging and therapy. In order to further understand their intrinsic emission nature, the temperature-dependent PL emissions of all the compounds from 300 to 80 K with a narrow interval of 20 K were also investigated. As illustrated in Figure 5, there are not any obvious changes of the emission positions for all compounds except that compound 1 shows a regular blueshift (710 → 690 nm) from 300 to 80 K. The intensities of maximum emission for all compounds monotonously increase with decreasing temperature and the broad emissions narrow significantly, which indicates the increased coupling interE


Article

Inorganic Chemistry

Figure 5. Temperature-dependent luminescent spectra of compounds 1 (a), 2 (b), 3 (c), and 4 (d) from 80 to 300 K.

Tables and figures of crystal data, additional experimental information, and characterization of compounds 1−4 (PDF)

very weak orange emissions centered at about 590 and 580 nm, respectively. Compared with the blue light emissions of organic cations, the red emission positions (711−801 nm) of compounds 1−4 are closer to those of CuX, AgI, and PbX2. Hence, the red light emissions of hybrid heterometallic halides 1−4 mainly originate from their inorganic skeletons. The slight differences of the emission peaks between the title compounds and bulk binary metal halides can be attributed to their structural differences in the hybrid heterometallic halides and the regulating effects of organic cations.

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Accession Codes

CCDC 1902180−1902181, 1902349, and 1902670 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ data_request/cif, or by emailing [email protected]. uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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CONCLUSIONS

In conclusion, we adopt the design strategy of combining the d10 transition and main group metals to construct a series of hybrid heterometallic halides with low-dimensional inorganic skeletons surrounded by organic cations. The combination of Cu+/Ag+ and Pb2+ metals in monophasic hybrid halides leads to strong red emissions with the largest Stocks shifts and fwhm, which are mainly derived from the inorganic semiconducting skeletons based on experimental and theoretical results. The successful constructions and red light emissions of the hybrid heterometallic halides indicate the design strategy of design new red or infrared luminescent materials in hybrid halide system. Further studies will be devoted to optimize their optical properties and probe into the relationship between crystal structures and PL emissions.

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AUTHOR INFORMATION

Corresponding Authors

*(Z.-H.J.) E-mail: [email protected]. *(X.-W.L.) E-mail: [email protected]. ORCID

Xiao-Wu Lei: 0000-0003-4603-9093 Author Contributions #

C.-Y.Y. and C.S. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We express thanks for the financial support from the National Nature Science Foundation of China (Nos. 21571081, 21671080 and 21601181), Fund of State Key Laboratory of Structural Chemistry (Nos. 20170011), a Project of Shandong Province Higher Educational Science and Technology Program (J18kz005), Laboratory Open Foundation of Qufu Normal University (sk201722), and the Cultivating Project for

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b01472. F


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Inorganic Chemistry

Zheng, W. X.; Qi, Y. J.; Zheng, S. T.; Yang, G. Y. Composite Hybrid Cluster Built from the Integration of Polyoxometalate and a Metal Halide Cluster: Synthetic Strategy, Structure, and Properties. Inorg. Chem. 2016, 55, 8257−8259. (c) Liu, J. H.; Gu, Y. N.; Chen, Y.; Qi, Y. J.; Li, X. X.; Zheng, S. T. Incorporating cuprous-halide clusters and lanthanide clusters to construct Heterometallic cluster organic frameworks with luminescence and gas adsorption properties. CrystEngComm 2018, 20, 738−745. (7) (a) Zhou, C. K.; Lin, H. R.; Lee, S. J.; Chaaban, M.; Ma, B. W. Organic−inorganic metal halide hybrids beyond perovskites. Mater. Res. Lett. 2018, 6, 552−569. (b) Yuan, Z.; Shu, Y.; Xin, Y.; Ma, B. W. Highly luminescent nanoscale quasi-2D layered lead bromide perovskites with tunable emissions. Chem. Commun. 2016, 52, 3887−3890. (c) Lei, X. W.; Yue, C. Y.; Wei, J. C.; Li, R. Q.; Mi, F. Q.; Li, Y.; Gao, L.; Liu, Q. X. Novel 3D Semiconducting OpenFrameworks based on Cuprous Bromides with Visible Light Driven Photocatalytic Properties. Chem. - Eur. J. 2017, 23, 14547−14553. (8) (a) Smith, M. D.; Karunadasa, H. I. White-Light Emission from Layered Halide Perovskites. Acc. Chem. Res. 2018, 51, 619−627. (b) Manser, J. S.; Christians, J. A.; Kamat, P. V. Intriguing Optoelectronic Properties of Metal Halide Perovskites. Chem. Rev. 2016, 116, 12956−13008. (c) Saparov, B.; Mitzi, D. B. Organic− Inorganic Perovskites: Structural Versatility for Functional Materials Design. Chem. Rev. 2016, 116, 4558−4596. (9) (a) García-Fernández, A.; Bermúdez-García, J. M.; CastroGarcía, S.; Llamas-Saiz, A. L.; Artiaga, R.; López-Beceiro, J. J.; Sánchez-Andújar, M.; Señarís-Rodríguez, M. A. [(CH3)2NH2]7Pb4X15 (X = Cl− and Br−), 2D-Perovskite Related Hybrids with Dielectric Transitions and Broadband Photoluminiscent Emission. Inorg. Chem. 2018, 57, 3215−3222. (b) Yang, X. G.; Ma, L. F.; Yan, D. P. Facile synthesis of 1D organic−inorganic perovskite micro-belts with high water stability for sensing and photonic applications. Chem. Sci. 2019, 10, 4567−4572. (10) (a) Peng, Y.; Yao, Y. P.; Li, L. N.; Wu, Z. Y.; Wang, S. S.; Luo, J. H. White-light emission in a chiral one-dimensional organic-inorganic hybrid perovskite. J. Mater. Chem. C 2018, 6, 6033−6037. (b) 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.; Schanze, K.; Clark, R.; Siegrist, T.; Ma, B. W. One-dimensional organic lead halide perovskites with efficient bluish white-light emission. Nat. Commun. 2017, 8, 14051. (c) Wang, S. S.; Yao, Y. P.; Kong, J. T.; Zhao, S. G.; Sun, Z. H.; Wu, Z. Y.; Li, L. N.; Luo, J. H. efficient white-light emission in a polar two-dimensional hybrid perovskite. Chem. Commun. 2018, 54, 4053−4056. (11) (a) Mao, L. L.; Wu, Y. L.; Stoumpos, C. C.; Wasielewski, M. R.; Kanatzidis, M. G. White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites. J. Am. Chem. Soc. 2017, 139, 5210−5215. (b) Hu, T.; Smith, M. D.; Dohner, E. R.; Sher, M. J.; Wu, X. X.; Trinh, M. T.; Fisher, A.; Corbett, J.; Zhu, X. Y.; Karunadasa, H. I.; Lindenberg, A. M. Mechanism for Broadband White-Light Emission from Two-Dimensional (110) Hybrid Perovskites. J. Phys. Chem. Lett. 2016, 7, 2258−2263. (c) Dohner, E. R.; Jaffe, A.; Bradshaw, L. R.; Karunadasa, H. I. Intrinsic White-Light Emission from Layered Hybrid Perovskites. J. Am. Chem. Soc. 2014, 136, 13154−13157. (12) (a) Zhou, C. K.; Lin, H. R.; Shi, H. L.; Tian, Y.; Pak, C.; Shatruk, M.; Zhou, Y.; Djurovich, P.; Du, M. H.; Ma, B. W. A ZeroDimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission. Angew. Chem., Int. Ed. 2018, 57, 1021−1024. (b) Lanzetta, L.; Marin-Beloqui, J. M.; Sanchez-Molina, I.; Ding, D.; Haque, S. A. Two-Dimensional Organic Tin Halide Perovskites with Tunable Visible Emission and Their Use in Light-Emitting Devices. ACS Energy Lett. 2017, 2, 1662−1668. (13) (a) Yangui, A.; Pillet, S.; Bendeif, E.; Lusson, A.; Triki, S.; Abid, Y.; Boukheddaden, K. Broadband Emission in a New TwoDimensional Cd-Based Hybrid Perovskite. ACS Photonics 2018, 5, 1599−1611. (b) Roccanova, R.; Houck, M.; Yangui, A.; Han, D.; Shi, H. L.; Wu, Y. T.; Glatzhofer, D. T.; Powell, D. R.; Chen, S. Y.; Fourati, H.; Lusson, A.; Boukheddaden, K.; Du, M. H.; Saparov, B.

Talent Team and Ascendant Subject of University in Shandong Province.

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REFERENCES

(1) (a) Zhou, J.; Xiao, H.; Zou, H. H.; Liu, X. A New Type of ThreeDimensional Hybrid Polymeric Haloplumbate Based on Rare HighNuclear Heterometallic Clusters. Inorg. Chem. 2018, 57, 12860− 12868. (b) Papagiannouli, I.; Maratou, E.; Koutselas, I.; Couris, S. Synthesis and Characterization of the Nonlinear Optical Properties of Novel Hybrid Organic-Inorganic Semiconductor Lead Iodide Quantum Wells and Dots. J. Phys. Chem. C 2014, 118, 2766−2775. (c) Daub, M.; Hillebrecht, H. Synthesis, Single-Crystal Structure and Characterization of (CH3NH3)2Pb(SCN)2I2. Angew. Chem., Int. Ed. 2015, 54, 11016−11017. (2) (a) Li, J. P.; Li, L. H.; Wu, L. M.; Chen, L. Synthesis, Properties, and Theoretical Studies of New Stepwise Layered Iodoplumbate: [Ni(opd)2(acn)2]n[Pb4I10]n. Inorg. Chem. 2009, 48, 1260−1262. (b) Gao, P.; Grätzel, M.; Nazeeruddin, M. K. Organohalide lead perovskites for photovoltaic Applications. Energy Environ. Sci. 2014, 7, 2448−2463. (c) Dang, Y. Y.; Ju, D. X.; Wang, L.; Tao, X. T. Recent progress in the synthesis of hybrid halide perovskite single crystals. CrystEngComm 2016, 18, 4476−4484. (d) Roccanova, R.; Ming, W. M.; Whiteside, V. R.; McGuire, M. A.; Sellers, I. R.; Du, M. H.; Saparov, B. Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH3NH3)2CdX4 (X = Cl, Br, I). Inorg. Chem. 2017, 56, 13878−13888. (3) (a) Stranks, S. D.; Snaith, H. J. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat. Nanotechnol. 2015, 10, 391−402. (b) Guo, Y. L.; Shoyama, K.; Sato, W.; Matsuo, Y.; Inoue, K.; Harano, K.; Liu, C.; Tanaka, H.; Nakamura, E. Chemical Pathways Connecting Lead(II) Iodide and Perovskite via Polymeric Plumbate(II) Fiber. J. Am. Chem. Soc. 2015, 137, 15907−15914. (c) Wang, G. E.; Xu, G.; Wang, M. S.; Cai, L. Z.; Li, W. H.; Guo, G. C. Semiconductive 3-D haloplumbate framework hybrids with high color rendering index white-light emission. Chem. Sci. 2015, 6, 7222−7226. (4) (a) Wang, M. S.; Guo, S. P.; Li, Y.; Cai, L. Z.; Zou, J. P.; Xu, G.; Zhou, W. W.; Zheng, F. K.; Guo, G. C. A Direct White-Light-Emitting Metal-Organic Framework with Tunable Yellow-to-White Photoluminescence by Variation of Excitation Light. J. Am. Chem. Soc. 2009, 131, 13572−13573. (b) Chen, W. T.; Wang, M. S.; Liu, X.; Huang, J. S.; et al. Investigations of Group 12 (IIB) Metal Halide/PseudohalideBipy Systems: Syntheses, Structures, Properties, and TDDFT Calculations (Bipy = 2,2‘-bipyridine or 4,4‘-bipyridine). Cryst. Growth Des. 2006, 6, 2289. (c) Wang, M. S.; Xu, G.; Zhang, Z. J.; Guo, G. C. Inorganic−organic hybrid photochromic materials. Chem. Commun. 2010, 46, 361. (d) Wang, M. S.; Guo, G. C.; Chen, W. T.; Xu, G.; Zhou, W. W.; Wu, K. J.; Huang, J. S. Angew. Chem., Int. Ed. 2007, 46, 3909−3911. (e) Wang, M. S.; Guo, G. C. Inorganic-organic hybrid white light phosphors. Chem. Commun. 2016, 52, 13194−13204. (5) (a) Wang, N.; Zhao, K. X.; Ding, T.; Liu, W. B.; Ahmed, A. S.; Wang, Z. R.; Tian, M. M.; Sun, X. W.; Zhang, Q. C. Improving Interfacial Charge Recombination in Planar Heterojunction Perovskite Photovoltaics with Small Molecule as Electron Transport Layer. Adv. Energy Mater. 2017, 7, 1700522. (b) Gu, P. Y.; Wang, N.; Wang, C. Y.; Zhou, Y. C.; Long, G. K.; Tian, M. M.; Chen, W. Q.; Sun, X. W.; Kanatzidis, M. G.; Zhang, Q. C. Pushing up the efficiency of planar perovskite solar cells to 18.2% with organic small molecules as the electron transport layer. J. Mater. Chem. A 2017, 5, 7339−7344. (c) Wang, N.; Liu, W. B.; Zhang, Q. C. Perovskite-Based Nanocrystals: Synthesis and Applications beyond Solar Cells. Small Methods 2018, 2, 1700380. (d) Nazarenko, O.; Kotyrba, M. R.; Yakunin, S.; Aebli, M.; Rainò, G.; Benin, B. M.; Wörle, M.; Kovalenko, M. V. Guanidinium-Formamidinium Lead Iodide: A Layered Perovskite-Related Compound with Red Luminescence at Room Temperature. J. Am. Chem. Soc. 2018, 140, 3850−3853. (6) (a) Li, X. X.; Wang, Y. X.; Wang, R. H.; Cui, C. Y.; Tian, C. B.; Yang, G. Y. Designed Assembly of Heterometallic Cluster Organic Frameworks Based on Anderson-Type Polyoxometalate Clusters. Angew. Chem., Int. Ed. 2016, 55, 6462−6466. (b) Li, X. X.; Ma, X.; G


Article

Inorganic Chemistry Broadband Emission in Hybrid Organic-Inorganic Halides of Group 12 Metals. ACS Omega 2018, 3, 18791−18802. (14) (a) Yang, S. M.; Lin, Z. H.; Wang, J. W.; Chen, Y. X.; Liu, Z. D.; Yang, E.; Zhang, J.; Ling, Q. D. High Color Rendering Index White-Light Emission from UV-Driven LEDs Based on Single Lumi ne scent Materi als: Two-Di mensional Pe rovs ki tes (C6H5C2H4NH3)2PbBrxCl4‑x. ACS Appl. Mater. Interfaces 2018, 10, 15980−15987. (b) Zhou, C. K.; Tian, Y.; Khabou, O.; Worku, M.; Zhou, Y.; Hurley, J.; Lin, H. R.; Ma, B. W. Manganese-Doped OneDimensional Organic Lead Bromide Perovskites with Bright White Emissions. ACS Appl. Mater. Interfaces 2017, 9, 40446−40451. (15) (a) Henary, M.; Zink, J. I. Photoluminescence of cubic mixedmetal tetrameric clusters. J. Am. Chem. Soc. 1989, 111, 7407−7411. (b) Bikas, R.; Hosseini-Monfared, H.; Vasylyeva, V.; Sanchiz, J.; Alonso, J.; Barandiaran, J. M.; et al. Heteronuclear mixed-metal Ag(I)−Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties. Dalton Trans. 2014, 43, 11925− 11935. (c) Wu, L.-M.; Wu, X.-T.; Chen, L. Structural overview and structure-property relationships of iodoplumbate and Iodobismuthate. Coord. Chem. Rev. 2009, 253, 2787−2804. (d) Fang, W.; Tang, C. Y.; Chen, R. H.; Jia, D. X.; Jiang, W. Q.; Zhang, Y. Polymeric heterometallic Pb−Ag iodometallates, iodoplumbates and iodoargentates with lanthanide complex cations as templates. Dalton Trans. 2013, 42, 15150−15158. (e) Guo, H. X.; Zhang, Y.; Li, X. Z.; Weng, W. Hydrothermal synthesis, crystal structure and optical properties of a 2-D heterometallic iodoplumbate. Inorg. Chem. Commun. 2010, 13, 425−428. (f) Nazarenko, O.; Kotyrba, M. R.; Wörle, M.; CuervoReyes, E.; Yakunin, S.; Kovalenko, M. V. Luminescent and Photoconductive Layered Lead Halide Perovskite Compounds Comprising Mixtures of Cesium and Guanidinium Cations. Inorg. Chem. 2017, 56, 11552−11564. (16) (a) Zhang, R. C.; Wang, J. J.; Yuan, B. Q.; Zhang, J. C.; Zhou, L.; Wang, H. B.; Zhang, D. J.; An, Y. L. Syntheses and Characterization of Chiral Zeolitic Silver Halides Based on 3-Rings. Inorg. Chem. 2016, 55, 11593−11599. (b) Liu, W.; Fang, Y.; Li, J. Copper Iodide Based Hybrid Phosphors for Energy-Efficient General Lighting Technologies. Adv. Funct. Mater. 2018, 28, 1705593. (c) Liu, J. W.; Feng, L.; Su, H. F.; Wang, Z.; Zhao, Q. Q.; Wang, X. P.; Tung, C. H.; Sun, D.; Zheng, L.-S. Anisotropic Assembly of Ag52 and Ag76 Nanoclusters. J. Am. Chem. Soc. 2018, 140, 1600−1603. (17) (a) Yue, C. Y.; Liu, F. L.; Deng, W. T.; Tao, J.; Hong, M. C. Iodide-Centered Cuprous Octatomic Ring: A Luminescent Molecular Thermometer Exhibiting Dual-Emission Character. Cryst. Growth Des. 2018, 18, 22−26. (b) Hupp, B.; Schiller, C.; Lenczyk, C.; Stanoppi, M.; Edkins, K.; Lorbach, A.; Steffen, A. Synthesis, Structures, and Photophysical Properties of a Series of Rare Near-IR Emitting Copper(I) Complexes. Inorg. Chem. 2017, 56, 8996−9008. (c) Zhang, Y.; Wu, T.; Liu, R.; Dou, T.; Bu, X. H.; Feng, P. Y. Three-Dimensional Photoluminescent Frameworks Constructed from Size-Tunable CuI Clusters. Cryst. Growth Des. 2010, 10, 2047−2049. (18) Sheldrick, G. M. SHELXTL; University of Gö ttingen: Göttingen, Germany, 2001. (19) (a) Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. First-principles simulation: Ideas, illustrations and the CASTEP code. J. Phys.: Condens. Matter 2002, 14, 2717−2744. (b) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865−3868. (c) Lin, J. S.; Qteish, A.; Payne, M. C.; Heine, V. Optimized and transferable nonlocal separable ab initiopseudopotentials. Phys. Rev. B: Condens. Matter Mater. Phys. 1993, 47, 4174− 4180. (20) (a) Fan, L. Q.; Wu, L. M.; Chen, L. Syntheses, Crystal Structures, and Properties of Heterometallic Iodoplumbates: Bicubane, Ribbon, and Chain Configurations. Inorg. Chem. 2006, 45, 3149−3151. (b) Burns, M. C.; Tershansy, M. A.; Ellsworth, J. M.; Khaliq, Z.; Peterson, L., Jr.; Smith, M. D.; zur Loye, H. C. Layered Heterometallic Iodoplumbate Containing a Novel Pb3Cu6I16 Net: Structure and Optical Properties. Inorg. Chem. 2006, 45, 10437−

10439. (c) Fan, L. Q.; Huang, Y. Z.; Wu, L. M.; Chen, L.; Li, J. Q.; Ma, E. PbI4Cu2(PPh3)4: A heterometallic iodide with unusual cisdivacant octahedral coordination sphere for lead: Synthesis, structure, red-infrared fluorescence and theoretical studies. J. Solid State Chem. 2006, 179, 2361−2366. (21) (a) Lei, X. W.; Yue, C. Y.; Wang, S.; Gao, H.; Wang, W.; Wang, N.; Yin, Y. D. Di-pyridyl Organic Cationic Directed Hybrid Cuprous Halogenides: Syntheses, Crystal Structures, Photochromism and Photocatalysis. Dalton Trans. 2017, 46, 4209−4217. (b) Lei, X. W.; Yue, C. Y.; Zhao, J. Q.; Han, Y. F.; Yang, J. T.; Meng, R. R.; Gao, C. S.; Ding, H.; Wang, C. Y.; Chen, W. D. Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties. Cryst. Growth Des. 2015, 15, 5416−5426. (22) Bondi, A. van der Waals Volumes and Radii. J. Phys. Chem. 1964, 68, 441−451. (23) Yue, C. Y.; Lei, X. W.; Han, Y. F.; Lu, X. X.; Tian, Y. W.; Xu, J.; Liu, X. F.; Xu, X. Transition-Metal-Complex Cationic Dyes Photosensitive to Two Types of 2D Layered Silver Bromides with Visible-Light-Driven Photocatalytic Properties. Inorg. Chem. 2016, 55, 12193−12203. (24) (a) Li, X. X.; Ha Do, T. T.; Granados del Á guila, A. G.; Huang, Y. J.; Chen, W. Q.; Li, Y. X.; Ganguly, R.; Morris, S.; Xiong, Q. H.; Li, D. S.; Zhang, Q. C. Two-Dimensional and Emission-Tunable: An Unusual Perovskite Constructed from Lindqvist-Type [Pb6Br19]7‑ Nanoclusters. Inorg. Chem. 2018, 57, 14035−14038. (b) Li, X. X.; Do, T. T. H.; Granados del Á guila, A. G.; Huang, Y. J.; Chen, W. Q.; Xiong, Q. H.; Zhang, Q. C. A 3D Haloplumbate Framework Constructed From Unprecedented Lindqvist-like Highly-Coordinated [Pb6Br25]13‑ Nanoclusters with Temperature-Dependent Emission. Chem. - Asian J. 2018, 13, 3185−3189. (25) (a) Wang, G. E.; Jiang, X. M.; Zhang, M. J.; Chen, H. F.; Liu, B. W.; Wang, M. S.; Guo, G. C. Crystal structures and optical properties of iodoplumbates hybrids templated by in situ synthesized 1,4diazabicyclo[2.2.2]octane derivatives. CrystEngComm 2013, 15, 10399−10404. (b) Zhang, Z. J.; Guo, G. C.; Xu, G.; Fu, M. L.; Zou, J. P.; Huang, J. S. [(H2 en)7(C2O4)2]n(Pb4I18)n·4nH2O, a New Type of Perovskite Co-templated by Both Organic Cations and Anions. Inorg. Chem. 2006, 45, 10028−10030. (26) (a) Shen, Y. L.; Lu, J. L.; Tang, C. Y.; Fang, W.; Jia, D. X.; Zhang, Y. Syntheses and properties of 2-D and 3-D Pb−Ag heterometallic iodides decorated with ethylene polyamines at the Pb(II) center. Dalton Trans. 2014, 43, 9116−9125. (b) Chai, W. X.; Wu, L. M.; Li, J. Q.; Chen, L. Silver Iodobismuthates: Syntheses, Structures, Properties, and Theoretical Studies of [Bi2Ag2I102‑]n and [Bi4Ag2I162‑]n. Inorg. Chem. 2007, 46, 1042−1044. (27) (a) Wu, G. H.; Zhou, C. K.; Ming, W. M.; Han, D.; Chen, S.; Yang, D.; Besara, T.; Neu, J.; Siegrist, T.; Du, M. H.; Ma, B. W.; Dong, A. A One-Dimensional Organic Lead Chloride Hybrid with Excitation-Dependent Broadband Emissions. ACS Energy Lett. 2018, 3, 1443−1449. (b) Fu, P. F.; Huang, M. L.; Shang, Y. Q.; Yu, N.; Zhou, H. L.; Zhang, Y. B.; Chen, S. Y.; Gong, J. K.; Ning, Z. J. Organic-Inorganic Layered and Hollow Tin Bromide Perovskite with Tunable Broadband Emission. ACS Appl. Mater. Interfaces 2018, 10, 34363−34369. (c) Zhou, C. K.; Worku, M.; Neu, J.; Lin, H. R.; Tian, Y.; Lee, S.; Zhou, Y.; Han, D.; Chen, S. Y.; Hao, A.; Djurovich, P. I.; Siegrist, T.; Du, M. H.; Ma, B. W. Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency. Chem. Mater. 2018, 30, 2374−2378. (d) Wang, S. S.; Yao, Y. P.; Wu, Z. Y.; Peng, Y.; Li, L. N.; Luo, J. H. Realization of “warm” white light via halide substitution in polar two-dimensional hybrid perovskites (2meptH2)PbClxBr4‑x. J. Mater. Chem. C 2018, 6, 12267−12272. (28) (a) Han, D.; Shi, H. L.; Ming, W. M.; Zhou, C. K.; Ma, B. W.; Saparov, B.; Ma, Y. Z.; Chen, S. Y.; Du, M. H. Unraveling luminescence mechanisms in zero-dimensional halide perovskites. J. Mater. Chem. C 2018, 6, 6398−6405. (b) Zhou, C. K.; Lin, H. R.; Tian, Y.; Yuan, Z.; Clark, R.; Chen, B. H.; van de Burgt, L. J.; Wang, J. C.; Zhou, Y.; Hanson, K.; Meisner, Q. J.; Neu, J.; Besara, T.; Siegrist, T.; Lambers, E.; Djurovich, P.; Ma, B. W. Luminescent zeroH


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