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

Abstract

The first post-synthetic solution-based crystal transformation of two-dimensional metal halide perovskites (2D MHPs) through organothiol-based reactions is reported. It is well-established that the crystal formation from a solution containing predesigned metal ion and organic cation precursors produces welldefined 2D MHPs with various intercalating organic cations. However, few reports outlining the post-synthetic crystal transformation on 2D MHPs have appeared. Here we report that, upon organothiol-based redox or condensation reactions, large organic cations in three types of 2D MHPs can convert to each other at ambient conditions without the damage of the layered inorganic framework. The swift and complete crystal interconversion has been confirmed using combined techniques including X-ray diffraction and 13 C-nuclear magnetic resonance spectroscopy. Electronic structures of the metal halide perovskites were investigated using computational chemistry.

Reduced-dimensional perovskites with dithioketal-containing intercalating cations for near-infrared light-emitting diodes

“…Both series of DJ phase MHPs were prepared using a one-step temperature-lowering crystal nucleation process optimized from the previous method. 1 The thioacetalization of the mercaptoethylammonium (MEA) precursor occurred simultaneously during the crystallization of the RD structure when the predesigned ketone (or aldehyde) was present, yielding PDSBA-based and MSBA-based MHP single crystals (PDSBA)(MA) n −1 Pb n I 3 n +1 and (MSBA)(MA) n −1 Pb n I 3 n +1 , where n = 1, 2, and 3, Fig. 1).…”

“…The recently introduced post-synthetic crystal conversion method via organothiol-based chemistry is a promising approach to explore new RD MHP structures. 1,18,19 The crystal formation and conversion are driven by the highly reactive thiol end groups on the intercalating cations, which can effectively convert to disulfide and dithioketal structures when interacting with oxidative reagents and ketones, respectively. In recent years, compared with traditional 3D perovskite, the operational stability of reduced dimensional (RD) perovskite and its optoelectronic devices has dramatically improved, attracting research interest worldwide.…”

0D/2D mixed-dimensional perovskite constructed by thiol- and disulfide-containing ligands

“…Herein, we report a new MD MHP, (MEA) 3 (DSBA)Pb 3 I 11 , which consists of two types of organic cations: mercaptoethylammonium (MEA) and 2,2′-disulfanediylbis(ethan-1-aminium) (DSBA). We demonstrated that the application of ketone adduct can partially oxidize MEA and generate DSBA ligand in situ, which effectively constructs the 0D/2D mixed structures in the precursor solution without initiating undesired competitive crystallization of 2D structures such as the previously reported (MEA) 2 PbI 4 and (DSBA)PbI 4 [22]. The MD structure consists of distorted 2D inorganic frameworks of [Pb 3 I 10 ] 4− layers of face-sharing [PbI 6 ] 4− octahedra and isolated 0D [Pb 3 I 12 ] 6− trimers of the same face-sharing octahedra.…”

“…The synthetic procedure of (DSBA)PbI 4 single crystals was altered from our previously reported recipe [22]. Briefly, 227.2 mg of MEACl (2.0 mmol) and 461.0 mg of PbI 2 (1.0 mmol) were dissolved in 1 ml of 57% w/w HI solution (7.6 mmol of HI) in a 10 ml thick-walled reaction tube with magnetic stirring.…”

The Effect of the Alkyl Chains of the Alkylammonium Pesudohalide Additives on the Performance of Dion Jacobson Perovskite Solar Cells

“…The low-dimensional metal halide perovskites that have been widely employed as the light-harvesting layer in HPSCs are mainly categorized into Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) types. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] RP perovskite materials have a staggered crystal structure (A' 2 A n−1 B n X 3n+1 ), where A' is a bulky monovalent alkyl or aromatic ammonium spacer cation and the inorganic layers are held together by the weak van der Waals force between the bilayer A' cations. DJ perovskite materials adopt an eclipsed crystal structure (A″A n−1 B n X 3n+1 ), where the diammonium cations A″ hold the inorganic layers together by forming hydrogen bonds.…”