Yi Xie, Heshan Hewa-Walpitage, Jack Morgenstein, Volker Blum, Zeev Valy Vardeny and David B. Mitzi*,
{"title":"二维过氧化物中的同手性和异手性阳离子混合,以增强结构不对称和自旋分裂能力","authors":"Yi Xie, Heshan Hewa-Walpitage, Jack Morgenstein, Volker Blum, Zeev Valy Vardeny and David B. Mitzi*, ","doi":"10.1021/acsmaterialslett.4c00558","DOIUrl":null,"url":null,"abstract":"<p >Overcoming the constraints of single-cation phases and further enhancing structural asymmetry represent critical objectives for optimizing emergent optoelectronic and spin-related properties in two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs). Here, we demonstrate homochiral (<i>S</i>/<i>S</i>) and heterochiral (<i>R</i>/<i>S</i>) cation mixing in 2D HOIPs via a 1:1 mixing of <i>S</i>- and <i>R</i>-4-bromo-α-methylbenzylammonium with <i>S</i>-1-methylhexyammonium. The <i>R</i>/<i>S</i> system achieves an enhanced structural asymmetry, marked by a significant Pb–I–Pb bond angle disparity (Δβ = 9.24°), attributed to the distinctive asymmetric templating effects from mixed cations with distinct molecular structures and opposite absolute configurations. Consequently, spin–orbit-coupled hybrid density functional theory (DFT) calculations indicate a substantial spin splitting (Δ<i>E</i> = 78.5 meV), among the largest reported for PbI<sub>4</sub><sup>2–</sup>-based 2D HOIPs. Nonequivalent chiral information from homo- and heterochiral mixing further modulates the Cotton effect for the same elemental composition. Our study demonstrates an important materials design strategy for enhancing structural asymmetry and advancing symmetry-breaking-reliant properties in organic–inorganic hybrids.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":null,"pages":null},"PeriodicalIF":9.6000,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Homochiral and Heterochiral Cation Mixing in 2D Perovskites for Enhanced Structural Asymmetry and Spin Splitting\",\"authors\":\"Yi Xie, Heshan Hewa-Walpitage, Jack Morgenstein, Volker Blum, Zeev Valy Vardeny and David B. Mitzi*, \",\"doi\":\"10.1021/acsmaterialslett.4c00558\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Overcoming the constraints of single-cation phases and further enhancing structural asymmetry represent critical objectives for optimizing emergent optoelectronic and spin-related properties in two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs). Here, we demonstrate homochiral (<i>S</i>/<i>S</i>) and heterochiral (<i>R</i>/<i>S</i>) cation mixing in 2D HOIPs via a 1:1 mixing of <i>S</i>- and <i>R</i>-4-bromo-α-methylbenzylammonium with <i>S</i>-1-methylhexyammonium. The <i>R</i>/<i>S</i> system achieves an enhanced structural asymmetry, marked by a significant Pb–I–Pb bond angle disparity (Δβ = 9.24°), attributed to the distinctive asymmetric templating effects from mixed cations with distinct molecular structures and opposite absolute configurations. Consequently, spin–orbit-coupled hybrid density functional theory (DFT) calculations indicate a substantial spin splitting (Δ<i>E</i> = 78.5 meV), among the largest reported for PbI<sub>4</sub><sup>2–</sup>-based 2D HOIPs. Nonequivalent chiral information from homo- and heterochiral mixing further modulates the Cotton effect for the same elemental composition. Our study demonstrates an important materials design strategy for enhancing structural asymmetry and advancing symmetry-breaking-reliant properties in organic–inorganic hybrids.</p>\",\"PeriodicalId\":19,\"journal\":{\"name\":\"ACS Materials Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.6000,\"publicationDate\":\"2024-06-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Materials Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsmaterialslett.4c00558\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Materials Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsmaterialslett.4c00558","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Homochiral and Heterochiral Cation Mixing in 2D Perovskites for Enhanced Structural Asymmetry and Spin Splitting
Overcoming the constraints of single-cation phases and further enhancing structural asymmetry represent critical objectives for optimizing emergent optoelectronic and spin-related properties in two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs). Here, we demonstrate homochiral (S/S) and heterochiral (R/S) cation mixing in 2D HOIPs via a 1:1 mixing of S- and R-4-bromo-α-methylbenzylammonium with S-1-methylhexyammonium. The R/S system achieves an enhanced structural asymmetry, marked by a significant Pb–I–Pb bond angle disparity (Δβ = 9.24°), attributed to the distinctive asymmetric templating effects from mixed cations with distinct molecular structures and opposite absolute configurations. Consequently, spin–orbit-coupled hybrid density functional theory (DFT) calculations indicate a substantial spin splitting (ΔE = 78.5 meV), among the largest reported for PbI42–-based 2D HOIPs. Nonequivalent chiral information from homo- and heterochiral mixing further modulates the Cotton effect for the same elemental composition. Our study demonstrates an important materials design strategy for enhancing structural asymmetry and advancing symmetry-breaking-reliant properties in organic–inorganic hybrids.
期刊介绍:
ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.