Postsynthetic Crystalline Transformation in Two-Dimensional Perovskites via Organothiol-Based Chemistry

Open AccessCCS ChemistryCOMMUNICATION11 May 2021Postsynthetic Crystalline Transformation in Two-Dimensional Perovskites via Organothiol-Based Chemistry Zilong Yuan†, Liang Zhao†, Ekadashi Pradhan, Ming Lai, Tao Zeng and Zhenyu Yang Yuan† MOE Laboratory of Bioinorganic Synthetic Chemistry, Lehn Institute Functional Materials, School Sun Yat-sen University, Guangzhou, Guangdong 510275 †Z. Yuan L. Zhao contributed equally to this work.Google Scholar More articles by author , Zhao† Pradhan Department York Toronto, ON M3J1P3 Google Lai *Corresponding author: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.021.202100929 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd favoritesTrack Citations ShareFacebookTwitterLinked InEmail The first postsynthetic solution-based crystal transformation two-dimensional metal halide perovskites (2D MHPs) through organothiol-based reactions is reported. It well-established that the formation from a solution containing predesigned ion organic cation precursors produces well-defined 2D MHPs with various intercalating cations. However, few reports outlining have appeared. Here, we report that, upon redox or condensation reactions, large cations three types can interconvert under ambient conditions without damage layered inorganic framework. swift complete interconversion has been confirmed using combined techniques including X-ray diffraction 13C nuclear magnetic resonance (13C NMR) spectroscopy. Electronic structures were investigated computational chemistry. Download figure PowerPoint Introduction Metal (MHPs) acclaimed as class promising semiconductor materials past decade because their compositionally tunable optoelectronic properties, high carrier mobility, simplicity fabrication.1–4 Advances managing compositions, surface passivating ligands adatoms, well progress device architecture encapsulation techniques, led rapid improvements performance perovskite-based optoelectronics.5–7 Conventional share three-dimensional (3D) pseudocubic structure (general chemical formula ABX3) which monovalent A (e.g., CH3NH3+ Cs+) are located voids created corner-sharing [BX6]4? octahedral When small A-site substituted organoammonium cations, Goldschmidt tolerance factor no longer within allowable regime thus octahedra isolated form (2D), structures. reduced dimensionality incorporation lead unrivaled tunability lattice photophysical properties MHPs.8–10 Recent demonstrated modulation design cations.11–14 Postsynthetic ligand engineering offers additional structural flexibility allows rational tailoring material characteristics. versatility widely applied classes such quantum dots metal–organic frameworks.15,16 Unfortunately, treatment methods not directly transferrable due weak van der Waals interaction between groups low energy liquid-like ionic structures.8 Till now, majority MHPs, regardless type thin film, powder, single crystal), prepared direct growth halides, (Figure 1).17–19 While there examples for MHP transformation,20,21 key contribution work realize methods. Additionally, characterized. Figure 1 | Schematic illustration preparation MHPs. In work, propose series fulfill achieved thiol, disulfide, dithioketal functional on For brevity, alkyl fragments connect thiol NH3+ shown. Noting reactivity organothiols, readily convert other groups, developed replacing mercaptoethylammonium (MEA) This facilitated efficient situ damaging original framework 1). reaction process relied thiols disulfide when interacting oxidative reagents acetone, respectively. We also successful conversion back at room temperature. these transformations spectroscopic (XRD) Results Discussion Initially, an optimized temperature-lowering spontaneous nucleation method prepare crystals: (MEA)2PbI4, (DSBA)PbI4, (PDSBA)PbI4, where MEA = SHCH2CH2NH3+, DSBA H3N+CH2CH2SSCH2CH2NH3+, PDSBA NH3+CH2CH2SC(CH3)2SCH2CH2NH3+ 2a). (MEA)2PbI4 (PDSBA)PbI4 reported time study 2a Supporting Information Figures S1 S3). As Louvain et al.22 two polymorphs, only synthesized ?-conformation polymorph, believed be more stable synthesis noticed use reductant hypophosphorous acid (H3PO2) necessary avoid undesired, oxidation (see Experimental Section). These morphologies colors 2b), geometrical parameters summarized Table 1. 2 Crystal (a) Single-crystal unit cells (PDSBA)PbI4. Only half cell shown clearer demonstration spatial configuration (b) Stereo Fluorescence Microscope (SFM) images crystals illumination visible 365-nm UV light. Single-Crystal Parameters Formula (DSBA)PbI4a system Orthorhombic Monoclinic Color Red Orange Space group Pnma P21/n Unit dimensions 12.9639 (3) Å 17.7855 (10) 8.5801 (17) b 20.5958 (5) 8.5500 (4) 54.936 (11) c 6.4283 (2) 23.270 8.6960 ? ? ? 90° 90°, 98.78 (1)° Volume (Å3) 1716.37 (8) 3497.11 (41) 4098.9 (14) Z 4 8 Density (g/cm3) 3.3371 3.301 2.953 aThe (DSBA)PbI4 CCDC no.: 724584.22 All similar ( S1–S3). inorganic–organic layers primarily dominated H atoms ammonium end I [PbI6]4? octahedra. average H···I bond lengths 2.60, 2.50, 2.64 S1–S3), respectively, shorter than summation Walls radii (?3.1 Å), reflecting hydrogen bonds. distortion degree layers, however, varies depending 178.5° I–Pb–I equatorial angles 175.9° Pb–I–Pb angles. comparison, 180° smaller 145.3° angles, those (I–Pb–I: 171.5° 139.2°). larger distortions latter attributed bonds atoms. difference arises orientations ligands. chains oriented parallel while vertical inserting toward Because both –NH3+ “head” –SH “tail” point interlayer space, distance adjacent 3.93 S1). S 3.66 S1), length organothiol molecules (1.8 Å?3.0 Å)23 matches times radius (?3.6 Å) S. reduced, yet relatively distance, together interactions hint atomic molecular dopants into lattice. next induced Inspired linkage organothiols,24 N-iodosuccinimide (NIS) oxidant (Path 3a). was monitored powder XRD (PXRD). Prior reaction, PXRD spectrum shows distinct patterns (0k0) orientation 3c). After NIS, signals disappear new found, (002) 3c S4). further NMR analysis dissolved deuterated dimethyl sulfoxide (DMSO-d6, 3b 3d). obvious differences shifts before after support hypothesis terminal oxidized NIS bond, generating situ. Neither crystalline nor found results, indicating byproducts. 3 transformation. representation four routes discussed study. Molecular MEA, DSBA, carbon labeled. (c–f) spectra following Paths A–D. unreacted marked triangles. solvent DMSO-d6 asterisks. full presented S5–S10. Motivated effective whether interact Ketone condensed organothiols forms linkages mild conditions.25 Therefore, explored potential acetone B 3a, see Section details). features emerge acetone-treated consistent spectrum, 27.0, 30.6, 39.2, 56.7 ppm indicate originating still sample 3c), conclude most transformed route, yielding crystal. Dithioketals commonly used protecting carbonyl-based they cleaved ketones.26 Similarly, converted soaking I2–dodecanethiol (1-DDT) mixed temperature 24 h C 3e, 3f, effectively cleaves C–S (Figures 3e 3f). speculate mechanism dithioketal-to-disulfide may involve dissociation promoted NIS27 subsequent S–S thiol-intermediate-driven condensation.28 To determine generality routes, tested effectiveness bromide Single (MEA)2PbBr4, (DSBA)PbBr4, (PDSBA)PbBr4 prepared, characterized, standard samples verify S11 observed (DSBA)PbBr4 S12). explain lack result SH···Br (MEA)2PbBr4 4). SH···X distances 2.94 2.73 former 0.21 larger, Br atom 0.13 I. Actually, just (3.05 Å). evident, consequence less activation S–H then difficult break forming S–C (PDSBA)PbBr4. Comparison closest bromine iodine (MEA)2PbI4. optical UV–vis absorption photoluminescence (PL) band gaps 2.02, 2.09, 2.18 eV, respectively 5a), slightly conventional butylammonium iodide [(BA)2PbI4] phenylethylammonium [(PEA)2PbI4].29 unexpected all gap narrowing reflected steady-state PL maxima, lower compared (BA)2PbI4 (PEA)2PbI4 S13).19,28–31 interesting note show strong longest lifetime decay value (?avg 3.29 ns, S14 S2), suggesting trap density slower charge-carrier recombination 5 Photophysical electronic (a b) Normalized normalized static-state (c) Fermi energies systems shifted 0 better comparison DOS pDOS panels (c). gain insight turned our focus calculated states (DOS) projected (pDOS) 5c. 1.95, 2.15, 2.20 eV They excellent agreement aforementioned bandgaps magnitudes sequence magnitudes. results clearly compounds conduction minimum (CBM) Pb. valence maximum (VBM) I, feature mixture contributions, especially edge absorptions must occur charge-transfer excitations 5a and5b regular Stokes shift emission anti-Stokes even logical associate Stokes-to-anti-Stokes change significant VBM. degenerate lone pair 5p orbitals VBM facilitate hole transfer Despite far transferred N migration I; cis 1–4 orbital overlap. Such separation electron quenches low-energy emissions CBM occurs wavelength absorption. Since quench ensues. Overall, frameworks likely extend exciton enhance conductivity. so-elongated explains > intensity S13). property now realized Moreover, overlaps different elucidate details spectra. peaks 5a. extends wave length, disappears beyond 460 nm. overlap Pb 0.5 above 0.3 below (middle panel 5c). transfers excited states, S, consequently shorten lifetimes high-energy eliminate corresponding emissions. does any until CBM, 0.4 (top range remain mostly recombine radiatively give <500 nm in-depth dynamics requires nonadiabatic simulations compounds, will addressed future Conclusion characterized single-crystal novel switching perovskite entirely solution-processed treatments destroying byproduct. composition confirm process. Furthermore, changes resulting characterizations simulations. demonstrates great MHPs: tuned maintaining skeleton. Quantum chemistry calculations revealed extents edges, available includes experimental sections, crystallographic data, spectra, bromide-based (PDF), data (CIF). Conflict Interest Competing interests: provisional patent application CN 202110140411.0 filed February 2, 2021 University. Notes Complete deposited Cambridge Crystallographic Data Centre (with numbers 2059317, 2059319, 2059316 2059318). obtained free www.ccdc.cam.ac.uk/data_request/cif Acknowledgments carried out Tianhe-2 (TH-2) super computer clusters (Guangzhou, Guangdong, China). Z.Y. would like acknowledge financial National Natural Science Foundation China (no. 21905316), Technology Province 2019QN01C108), Profs. P. Hu, T. Zhu, Z. W. Wei thanked valuable suggestions. T.Z. thanks University start-up grant 481333) Sciences Engineering Research Council (NSERC) Canada RGPIN-2016-06276) support. References Cao D. H.; Stoumpos C. C.; Farha O. K.; Hupp J. T.; Kanatzidis M. 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