Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites
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...
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| Veröffentlicht in: | Journal of the American Chemical Society 2023-08, Vol.145 (32), p.17831-17844 |
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| creator | Xie, Yi Morgenstein, Jack Bobay, Benjamin G. Song, Ruyi Caturello, Naidel A. M. S. Sercel, Peter C. Blum, Volker Mitzi, David B. |
| description | 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 ( |
| doi_str_mv | 10.1021/jacs.3c04832 |
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M. S. ; Sercel, Peter C. ; Blum, Volker ; Mitzi, David B.</creator><creatorcontrib>Xie, Yi ; Morgenstein, Jack ; Bobay, Benjamin G. ; Song, Ruyi ; Caturello, Naidel A. M. S. ; Sercel, Peter C. ; Blum, Volker ; Mitzi, David B. ; Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE)</creatorcontrib><description>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 levelspecifically, 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.</description><identifier>ISSN: 0002-7863</identifier><identifier>ISSN: 1520-5126</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.3c04832</identifier><identifier>PMID: 37531203</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>cations ; Chemistry ; circular dichroism spectroscopy ; density functional theory ; energy ; nuclear magnetic resonance spectroscopy ; temperature</subject><ispartof>Journal of the American Chemical Society, 2023-08, Vol.145 (32), p.17831-17844</ispartof><rights>2023 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a384t-f447dead3c9d02691e35b99ec53d8eaccdc6da5c9e28df1d96df7eba16d1b9da3</citedby><cites>FETCH-LOGICAL-a384t-f447dead3c9d02691e35b99ec53d8eaccdc6da5c9e28df1d96df7eba16d1b9da3</cites><orcidid>0000-0002-0320-7803 ; 0000-0002-0147-9514 ; 0000-0001-5189-4612 ; 0000-0002-1734-3793 ; 0000-0001-8660-7230 ; 0000000217343793 ; 0000000151894612 ; 0000000186607230 ; 0000000203207803 ; 0000000201479514</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jacs.3c04832$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jacs.3c04832$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2751,27055,27903,27904,56717,56767</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37531203$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/2424976$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Xie, Yi</creatorcontrib><creatorcontrib>Morgenstein, Jack</creatorcontrib><creatorcontrib>Bobay, Benjamin G.</creatorcontrib><creatorcontrib>Song, Ruyi</creatorcontrib><creatorcontrib>Caturello, Naidel A. M. S.</creatorcontrib><creatorcontrib>Sercel, Peter C.</creatorcontrib><creatorcontrib>Blum, Volker</creatorcontrib><creatorcontrib>Mitzi, David B.</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE)</creatorcontrib><title>Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>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 levelspecifically, 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.</description><subject>cations</subject><subject>Chemistry</subject><subject>circular dichroism spectroscopy</subject><subject>density functional theory</subject><subject>energy</subject><subject>nuclear magnetic resonance spectroscopy</subject><subject>temperature</subject><issn>0002-7863</issn><issn>1520-5126</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNqFkUtLAzEUhYMotlZ3rmVw5cLRvOaRpUx9FCoK1XXIJBk7dWZSk4zQf2-GVt0Iri7n8t1z4RwAThG8QhCj65WQ7opISHOC98AYJRjGCcLpPhhDCHGc5SkZgSPnVkFSnKNDMCJZQhCGZAxmxbK2ookK4WvTRVOzrru3qDI2ejSqb8I2yIW3vfT9wC02bau93USmivA0etbWfLr32mt3DA4q0Th9spsT8Hp3-1I8xPOn-1lxM48FyamPK0ozpYUikimIU4Y0SUrGtEyIyrWQUslUiUQyjXNVIcVSVWW6FChVqGRKkAk43_oa52vuZPgtl9J0nZaeY4opy9IAXWyhtTUfvXaet7WTumlEp03vOIEUUsowzv5FcU4TFGBIAnq5RaU1zlld8bWtW2E3HEE-lMGHMviujICf7Zz7stXqB_5O__f1cLUyve1CcH97fQGow5J2</recordid><startdate>20230816</startdate><enddate>20230816</enddate><creator>Xie, Yi</creator><creator>Morgenstein, Jack</creator><creator>Bobay, Benjamin G.</creator><creator>Song, Ruyi</creator><creator>Caturello, Naidel A. 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S.</creator><creator>Sercel, Peter C.</creator><creator>Blum, Volker</creator><creator>Mitzi, David B.</creator><general>American Chemical Society</general><general>American Chemical Society (ACS)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-0320-7803</orcidid><orcidid>https://orcid.org/0000-0002-0147-9514</orcidid><orcidid>https://orcid.org/0000-0001-5189-4612</orcidid><orcidid>https://orcid.org/0000-0002-1734-3793</orcidid><orcidid>https://orcid.org/0000-0001-8660-7230</orcidid><orcidid>https://orcid.org/0000000217343793</orcidid><orcidid>https://orcid.org/0000000151894612</orcidid><orcidid>https://orcid.org/0000000186607230</orcidid><orcidid>https://orcid.org/0000000203207803</orcidid><orcidid>https://orcid.org/0000000201479514</orcidid></search><sort><creationdate>20230816</creationdate><title>Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites</title><author>Xie, Yi ; Morgenstein, Jack ; Bobay, Benjamin G. ; Song, Ruyi ; Caturello, Naidel A. M. S. ; Sercel, Peter C. ; Blum, Volker ; Mitzi, David B.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a384t-f447dead3c9d02691e35b99ec53d8eaccdc6da5c9e28df1d96df7eba16d1b9da3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>cations</topic><topic>Chemistry</topic><topic>circular dichroism spectroscopy</topic><topic>density functional theory</topic><topic>energy</topic><topic>nuclear magnetic resonance spectroscopy</topic><topic>temperature</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Xie, Yi</creatorcontrib><creatorcontrib>Morgenstein, Jack</creatorcontrib><creatorcontrib>Bobay, Benjamin G.</creatorcontrib><creatorcontrib>Song, Ruyi</creatorcontrib><creatorcontrib>Caturello, Naidel A. M. S.</creatorcontrib><creatorcontrib>Sercel, Peter C.</creatorcontrib><creatorcontrib>Blum, Volker</creatorcontrib><creatorcontrib>Mitzi, David B.</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>OSTI.GOV</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Xie, Yi</au><au>Morgenstein, Jack</au><au>Bobay, Benjamin G.</au><au>Song, Ruyi</au><au>Caturello, Naidel A. M. S.</au><au>Sercel, Peter C.</au><au>Blum, Volker</au><au>Mitzi, David B.</au><aucorp>Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2023-08-16</date><risdate>2023</risdate><volume>145</volume><issue>32</issue><spage>17831</spage><epage>17844</epage><pages>17831-17844</pages><issn>0002-7863</issn><issn>1520-5126</issn><eissn>1520-5126</eissn><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 levelspecifically, 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.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>37531203</pmid><doi>10.1021/jacs.3c04832</doi><tpages>14</tpages><orcidid>https://orcid.org/0000-0002-0320-7803</orcidid><orcidid>https://orcid.org/0000-0002-0147-9514</orcidid><orcidid>https://orcid.org/0000-0001-5189-4612</orcidid><orcidid>https://orcid.org/0000-0002-1734-3793</orcidid><orcidid>https://orcid.org/0000-0001-8660-7230</orcidid><orcidid>https://orcid.org/0000000217343793</orcidid><orcidid>https://orcid.org/0000000151894612</orcidid><orcidid>https://orcid.org/0000000186607230</orcidid><orcidid>https://orcid.org/0000000203207803</orcidid><orcidid>https://orcid.org/0000000201479514</orcidid></addata></record> |
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| subjects | cations Chemistry circular dichroism spectroscopy density functional theory energy nuclear magnetic resonance spectroscopy temperature |
| title | Chiral Cation Doping for Modulating Structural Symmetry of 2D Perovskites |
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