skip to main content

Title: One-dimensional organic metal halide nanoribbons with dual emission
Organic metal halide hybrids with low-dimensional structures at the molecular level have received great attention recently for their exceptional structural tunability and unique photophysical properties. Here we report for the first time the synthesis and characterization of a one-dimensional (1D) organic metal halide hybrid, which contains metal halide nanoribbons with a width of three octahedral units. It is found that this material with a chemical formula C 8 H 28 N 5 Pb 3 Cl 11 shows a dual emission with a photoluminescence quantum efficiency (PLQE) of around 25%. Photophysical studies and density functional theory (DFT) calculations suggest the coexisting of delocalized free excitons and localized self-trapped excitons in metal halide nanoribbons leading to the dual emission.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Communications
Page Range / eLocation ID:
3711 to 3714
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials. However, the origin of the photoluminescence (PL) and, in particular, the different photophysical properties in hybrid organic–inorganic and all inorganic halides are still poorly understood. In this work, first-principles calculations were performed to study the excitons and intrinsic defects in 0D hybrid organic–inorganic halides (C 4 N 2 H 14 X) 4 SnX 6 (X = Br, I), which exhibit a high photoluminescence quantum efficiency (PLQE) at room temperature (RT), and also in the 0D inorganic halide Cs 4 PbBr 6 , which suffers from strong thermal quenching when T > 100 K. We show that the excitons in all three 0D halides are strongly bound and cannot be detrapped or dissociated at RT, which leads to immobile excitons in (C 4 N 2 H 14 X) 4 SnX 6 . However, the excitons in Cs 4 PbBr 6 can still migrate by tunneling, enabled by the resonant transfer of excitation energy (Dexter energy transfer). The exciton migration in Cs 4 PbBr 6 leads to a higher probability of trapping and nonradiative recombination at the intrinsic defects. We show that a large Stokes shift and the negligible electronic coupling between luminescent centers are important for suppressing exciton migration; thereby, enhancing the photoluminescence quantum efficiency. Our results also suggest that the frequently observed bright green emission in Cs 4 PbBr 6 is not due to the exciton or defect-induced emission in Cs 4 PbBr 6 but rather the result of exciton emission from CsPbBr 3 inclusions trapped in Cs 4 PbBr 6 . 
    more » « less
  2. Abstract

    Mechanochemical synthesis has emerged as a facile method for the preparation of a wide range of organic, inorganic, and polymeric materials. Here, we report the use of mechanochemical synthesis for the preparation of ionically bonded organic metal halide hybrids with a zero‐dimensional (0D) structure at the molecular level. (Ph4P)2SbCl5and (Ph4P)2MnCl4were synthesized by grinding appropriate ratios of organic halide salt Ph4PCl with inorganic metal halide salts SbCl3and MnCl2, respectively. The structural and photophysical properties of mechanochemically synthesized (Ph4P)2SbCl5and (Ph4P)2MnCl4were characterized, which are almost identical to those of single crystals prepared by slow solution growth. By reacting Ph4PCl with both SbCl3and MnCl2, we have been able to produce a mixture of two 0D organic metal halide hybrids that exhibit a dual emission covering a wide range of the spectrum with Commission Internationale de l'Eclairage (CIE) coordinates of (0.4898, 0.4800). Our work has clearly established mechanochemical synthesis as an effective method to produce ionically bonded organic‐inorganic hybrids.

    more » « less
  3. The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6 H 13 N 4 ) 3 Pb 2 Br 7 . In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2 Br 9 5− ) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6 H 13 N 4 + ). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ∼7%. Having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials. 
    more » « less
  4. Abstract

    The family of molecular level low‐dimensional organic metal halide hybrids has expanded significantly over the last few years. Here a new type of 1D metal halide structure is reported, in which metal halide octahedra form a corrugated double‐chain structure via nonplanar edge‐sharing. This material with a chemical formula of C5H16N2Pb2Br6exhibits a broadband yellow emission under ultraviolet light excitation with a photoluminescence quantum efficiency of around 10%. The light‐yellow emission is considered to be attributed to self‐trapping excitons. Theoretical calculations show that the unique alignment of the octahedra leads to small band dispersion and large exciton binding energy. Together with previously reported 1D metal halide wires and tubes, this new bulk assembly of 1D metal halides suggests the potential to develop a library of bulk assemblies of metal halides with controlled structures and compositions.

    more » « less
  5. Abstract

    The synthesis and characterization is reported of (C9NH20)2SnBr4, a novel organic metal halide hybrid with a zero‐dimensional (0D) structure, in which individual seesaw‐shaped tin (II) bromide anions (SnBr42−) are co‐crystallized with 1‐butyl‐1‐methylpyrrolidinium cations (C9NH20+). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep‐red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr42−species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.

    more » « less