Ordered Mixed-Spacer 2D Bromide Perovskites and the Dual Role of 1,2,4-Triazolium Cation

Xiaotong Li (1) , Hao Dong (2) , George Volonakis (3) , Constantinos Stoumpos (4) , Jacky Even (5) , Claudine Katan (3) , Peijun Guo (2) , Mercouri Kanatzidis (1)

1 Department of Chemistry [Northwestern University]
2 Yale University [New Haven]
3 ISCR - Institut des Sciences Chimiques de Rennes
4 UOC - University of Crete [Heraklion]
5 FOTON - Institut des Fonctions Optiques pour les Technologies de l'informatiON

Two-dimensional (2D) halide perovskites exhibit extraordinary stability and structural diversity because they can incorporate different organic cations (both cage A-site cation and the spacer). Here we report on the behavior of Tz = 1,2,4-triazolium as an A-site cation as well as a spacer cation in new perovskite compounds. We describe the synthesis and structure-property relationships of a new family of hydrogen-bonding stabilized 2D perovskites, (IPA)2(Tz)n-1PbnBr3n+1 (n = 1-3) (IPA = isopropylammonium, Tz = 1,2,4-triazolium), which represents the rare example of 2D perovskites incorporating large A-site cation (Tz) that can form both the n = 2 and 3 phases. However, excess of Tz cations can split the n = 2 layers to act as spacer, and combine with another spacer PA (PA = propylammonium) or BA (BA = butylammonium) to form n = 1 structures (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4. These ordered mixed-spacer perovskites with different interlayer distances are unusual because the different spacers tend to stay in the same interlayer. (IPA)2(Tz)n-1PbnBr3n+1 all exhibit broad photoluminescence (PL) emission, but for different reasons. For the n = 1 phase, the large octahedral tilting (small Pb-Br-Pb angle) gives rise to the broad emission, while for the n = 2 and 3 phases, the individual octahedral distortion (large distortion index) plays a more important role. For the mixed-spacer (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4, their bandgaps are in between the parent n = 1 compounds ((BA)2PbBr4 or (PA)2PbBr4 , and (Tz)2PbBr4). DFT calculations suggest that the band structures of (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4 combine features from both parent compounds yet differ from a simple superposition. This work demonstrates the dual role of Tz molecules as the A-site cation in multilayer 2D perovskites and as the spacer in ordered mixed-spacer 2D phases.

Domaines: Chimie théorique et/ou physique

Xiaotong Li, Hao Dong, George Volonakis, Constantinos Stoumpos, Jacky Even, et al.. Ordered Mixed-Spacer 2D Bromide Perovskites and the Dual Role of 1,2,4-Triazolium Cation. Chemistry of Materials, 2022, 34 (14), pp.6541-6552. ⟨10.1021/acs.chemmater.2c01432⟩. ⟨hal-03726767⟩