Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites.

Abstract

Cation mixing in two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) structures represents an important degree of freedom for modifying organic templating effects and tailoring inorganic structures. However, the limited number of known cation-mixed 2D HOIP systems generally employ a 1:1 cation ratio for stabilizing the 2D perovskite structure. Here, we demonstrate a chiral-chiral mixed-cation system wherein a controlled small amount (<10%) of chiral cation S-2-MeBA (S-2-MeBA = (S)-(-)-2-methylbutylammonium) can be doped into (S-BrMBA)2PbI4 (S-BrMBA = (S)-(-)-4-bromo-α-methylbenzylammonium), modulating the structural symmetry from a higher symmetry (C2) to the lowest symmetry state (P1). This structural change occurs when the concentration of S-2-MeBA, measured by solution nuclear magnetic resonance, exceeds a critical level─specifically, for 1.4 ± 0.6%, the structure remains as C2, whereas 3.9 ± 1.4% substitution induces the structure change to P1 (this structure is stable to ∼7% substitution). Atomic occupancy analysis suggests that one specific S-BrMBA cation site is preferentially substituted by S-2-MeBA in the unit cell. Density functional theory calculations indicate that the spin splitting along different k-paths can be modulated by cation doping. A true circular dichroism band at the exciton energy of the 3.9% doping phase shows polarity inversion and a ∼45 meV blue shift of the Cotton-effect-type line-shape relative to (S-BrMBA)2PbI4. A trend toward suppressed melting temperature with higher doping concentration is also noted. The chiral cation doping system and the associated doping-concentration-induced structural transition provide a material design strategy for modulating and enhancing those emergent properties that are sensitive to different types of symmetry breaking.

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Published Version (Please cite this version)

10.1021/jacs.3c04832

Publication Info

Xie, Yi, Jack Morgenstein, Benjamin G Bobay, Ruyi Song, Naidel AMS Caturello, Peter C Sercel, Volker Blum, David B Mitzi, et al. (2023). Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites. Journal of the American Chemical Society, 145(32). pp. 17831–17844. 10.1021/jacs.3c04832 Retrieved from https://hdl.handle.net/10161/28917.

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Scholars@Duke

Bobay

Benjamin Bobay

Assistant Professor in Radiology

I am the Assistant Director of the Duke University NMR Center and an Assistant Professor in the Duke Radiology Department. I was originally trained as a structural biochemist with an emphasis on utilizing NMR and continue to use this technique daily helping collaborators characterize protein structures and small molecules through a diverse set of NMR experiments. Through the structural characterization of various proteins, from both planta and eukaryotes, I have developed a robust protocol of utilizing computational biology for describing binding events, mutations, post-translations modifications (PTMs), and/or general behavior within in silico solution scenarios. I have utilized these techniques in collaborations ranging from plant pathologists at the Swammerdam Institute for Life Sciences department at the University of Amsterdam to biomedical engineers at North Carolina State University to professors in the Pediatrics department at Duke University. These studies have centered around the structural and functional consequences of PTMs (such as phosphorylation), mutation events, truncation of multi-domain proteins, dimer pulling experiments, to screening of large databases of ligands for potential binding events. Through this combination of NMR and computational biology I have amassed 50 peer-reviewed published articles and countless roles on scientific projects, as well as the development of several tutorials concerning the creation of ligand databases and high-throughput screening of large databases utilizing several different molecular dynamic and computational docking programs.

Blum

Volker Blum

Rooney Family Associate Professor of Mechanical Engineering and Materials Science

Volker Blum heads the "Ab initio materials simulations" group at Duke University. Dr. Blum's research focuses on first-principles computational materials science: using the fundamental laws of quantum mechanics to predict the properties of real materials from the atomic scale on upwards.

Specific focus areas are interface and nanoscale systems with electronic and energy applications, as well as work on molecular structure and spectroscopy. He is actively working on novel semiconductor materials, including hybrid organic-inorganic perovskites and complex chalcogenide materials. Both groups of materials hold promise as absorbers for photovoltaics (i.e., solar cells), as materials for spin-based electronics and optoelectronics, and other semiconductor applications.

Dr. Blum is the coordinator of a major computer package for computational materials and molecular science based on electronic structure theory, FHI-aims. Work in his group is interdisciplinary (touching areas of physics and chemistry in addition to materials science), with opportunities for international collaboration and exchange.


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