Chiral Molecules Induce Enantiomorphic Lattice Helicity in Chiral 0D Tin Bromide Crystals
Abstract
AbstractChiral organic–inorganic hybrid metal halides have emerged as a promising class of materials for spin‐controlled optical and optoelectronic effects and related applications. Chiral hybrid metal halides generally crystallize in non‐helical space groups. Herein, we report the discovery of zero‐dimensional (0D) chiral (R/S‐MBA)2SnBr6 (MBA: methylbenzylammonium cation) single crystals with enantiomorphic lattice helicity. The S‐enantiomer of the chiral molecule induces right‐handed helicity with the P61 space group (right‐handed, P‐helix), while the R‐enantiomer induces right‐handed helicity with the P65 space group (left‐handed, M‐helix). The chiral molecules induce the helical twist of inorganic units in the lattice through N─H···Br and C─H···π interactions. Density functional theory (DFT) calculations indicate that the strong electronic coupling between chiral molecules and SnBr62− subunits is responsible for the generation of chirality. The chiral crystals exhibit circular dicroism (CD) spectra with a high dissymmetry factor (gCD) of 3.5 × 10−2 and no Cotton effect, maintaining the same CD sign throughout the spectrum. In addition, they exhibit broadband second harmonic generation (SHG) over a broad excitation range, with a gCP‐SHG up to 0.44. Furthermore, we find that the alloying of Sn with Pb leads to a change in dimensionality from 0D to non‐helical 1D structures. These crystals with helical lattices and interesting CD responses are expected to open new avenues for spin‐controlled applications.
Article Details
Authors (14)
Ramavath Babu
CINBIO Universidade de Vigo, Department of Physical Chemistry Campus Universitario As Lagoas‐Marcosende Universidade de Vigo Vigo 36310 Spain
Haoyuan Xu
Guangdong Basic Research Center of Excellence for Structure and Fundamental Interactions of Matter Guangdong Provincial Key Laboratory of Quantum Engineering and Quantum Material School of Physics South China Normal University Guangzhou 510006 China
Berta Covelo
CACTI Campus Universitario As Lagoas‐Marcosende Universidade de Vigo Vigo 36310 Spain
Ignacio Pérez‐Juste
Department of Physical Chemistry Campus Universitario As Lagoas‐Marcosende Universidade de Vigo Vigo 36310 Spain
Julian E. Heger
TUM School of Natural Sciences, Chair for Functional Materials, Physics Department, Technical University of Munich, James-Franck-Str. 1, 85748 Garching, Germany
Nasrin Solhtalab
Physikalisch‐Chemisches Institut Universität Heidelberg Im Neuenheimer Feld 229 69120 Heidelberg Germany
Zelin Li
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, ECNU Engineering Center for Sustainable Carbon, School of Chemistry and Molecular Engineering
Longfeng Zhong
Guangdong Basic Research Center of Excellence for Structure and Fundamental Interactions of Matter Guangdong Provincial Key Laboratory of Quantum Engineering and Quantum Material School of Physics South China Normal University Guangzhou 510006 China
Xiaowen Hu
Felix Deschler
Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg, Germany
Peter Müller‐Buschbaum
TUM School of Natural Sciences Department of Physics Chair for Functional Materials Technical University of Munich James‐Franck‐Str. 1 85748 Garching Germany
Xiao‐Fang Jiang
Guangdong Basic Research Center of Excellence for Structure and Fundamental Interactions of Matter Guangdong Provincial Key Laboratory of Quantum Engineering and Quantum Material School of Physics South China Normal University Guangzhou 510006 China
Sergio Gómez‐Graña
CINBIO, Universidade de Vigo, Department of Physical Chemistry Campus Universitario As Lagoas‐Marcosende Universidade Devigo Vigo Spain
Lakshminarayana Polavarapu
CINBIO, Universidade de Vigo, Department of Physical Chemistry Campus Universitario As Lagoas‐Marcosende Universidade Devigo Vigo Spain