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The templating role in the formation of 2D metal halide perovskites of diammonium cations, such as 1,3-phenylenediammonium, 1,3-xylylenediammonium, 1,4-phenylenediammonium, and 1,4-xylylenediammonium cations, has been investigated.

The role of templating the formation of 2D metal halide perovskites has been investigated by considering the 1,3-phenylenediammonium (1,3-PDA), 1,3-xylylenediamimonium (1,3-XDA), 1,4-phenylenediammonium (1,4-PDA), and 1,4-xylylenediamimonium (1,4-XDA) cations in lead bromide systems. Single-crystal x-ray diffraction confirms the formation 2D Dion-Jacobons (DJ) perovskites for all the cations except for the 1,3-XDA cation leading to a so-called 0D perovskitoid. Analysis of the structural data showed a higher distortion degree for the systems containing the shorter cation, namely 1,4-PDA. A detailed spectroscopic investigation, with both static and time resolved photoluminescence spectroscopy, revealed a broadband emissive component at room temperature with hundreds of nanometers of bandwidth when 1,3-PDA and 1,4-PDA cations are present, while a narrow peak is found for the longer cation, i.e. 1,4-XDA. A broadband emission arises in this last sample as well by decreasing temperature. Such broad emission, as indicated by the analysis of the power and temperature dependence of the PL, can be attributed to trap-mediated excitonic recombination or STEs, and the trend in emissive properties can be correlated to the different level of octahedral distortions. The novel systems reported in this work enlarge the family of broadband emitters and add further clues to develop efficient perovskite-based broadband and white light emitters.

We devised a hot-injection synthesis to prepare colloidal double-perovskite Cs2NaBiCl6 nanocrystals (NCs). We also examined the effects of replacing Na+ with Ag+ cations by preparing and characterizing Cs2Na1-x Ag x BiCl6 alloy NCs with x ranging from 0 to 1. Whereas Cs2NaBiCl6 NCs were not emissive, Cs2Na1-x Ag x BiCl6 NCs featured a broad photoluminescence band at ∼690 nm, Stokes-shifted from the respective absorption by ≥1.5 eV. The emission efficiency was maximized for low Ag+ amounts, reaching ∼3% for the Cs2Na0.95Ag0.05BiCl6 composition. Density functional theory calculations coupled with spectroscopic investigations revealed that Cs2Na1-x Ag x BiCl6 NCs are characterized by a complex photophysics stemming from the interplay of (i) radiative recombination via trapped excitons localized in spatially connected AgCl6-BiCl6 octahedra; (ii) surface traps, located on undercoordinated surface Bi centers, behaving as phonon-assisted nonradiative decay channels; and (iii) a thermal equilibrium between trapping and detrapping processes. These results offer insights into developing double-perovskite NCs with enhanced optoelectronic efficiency.