Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms
Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representat...
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| Veröffentlicht in: | Chemphyschem 2024-01, Vol.25 (2), p.e202300064-n/a |
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| creator | Xu, Yunyao Chen, Jia Aydt, Alexander P. Zhang, Lichirui Sergeyev, Ivan Keeler, Eric G. Choi, Bonnie He, Shoushou Reichman, David R. Friesner, Richard A. Nuckolls, Colin Steigerwald, Michael L. Roy, Xavier McDermott, Ann E. |
| description | Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6Se8(PEt3)6. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6Se8] core while ligands function as an insulated shell. 59Co SSNMR measurements on the core and 31P, 13C on the ligands show that the neutral Co6Se8(PEt3)6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6Se8(PEt3)6]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.
Multinuclear NMR and quantum calculation reveal the atom‐like feature of a metal chalcogenide cluster, a superatom as the valence electrons/spins delocalize over the entire inorganic core and are insulated by its ligand shell. |
| doi_str_mv | 10.1002/cphc.202300064 |
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Multinuclear NMR and quantum calculation reveal the atom‐like feature of a metal chalcogenide cluster, a superatom as the valence electrons/spins delocalize over the entire inorganic core and are insulated by its ligand shell.</description><identifier>ISSN: 1439-4235</identifier><identifier>EISSN: 1439-7641</identifier><identifier>DOI: 10.1002/cphc.202300064</identifier><identifier>PMID: 38057144</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Aromaticity ; cluster aromaticity ; Diamagnetism ; Electron spin ; Electronic structure ; Ligands ; Magnetic properties ; Molecular clusters ; Molecular orbitals ; NMR ; Nuclear magnetic resonance ; Paramagnetism ; quantum calculations ; spin/electron delocalization ; SSNMR ; superatomic solid</subject><ispartof>Chemphyschem, 2024-01, Vol.25 (2), p.e202300064-n/a</ispartof><rights>2023 Wiley‐VCH GmbH</rights><rights>2023 Wiley-VCH GmbH.</rights><rights>2024 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c3124-f4652014171fafb3e83de8985af78094e264d2b115c6f8e692279d59fa88f5cd3</cites><orcidid>0000-0002-9249-1649 ; 0000-0001-5587-4854 ; 0000-0002-0384-5493 ; 0000-0001-6587-9528 ; 0000-0002-5265-5637 ; 0000-0002-8850-0725 ; 0000-0002-9598-7148</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fcphc.202300064$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fcphc.202300064$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38057144$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Xu, Yunyao</creatorcontrib><creatorcontrib>Chen, Jia</creatorcontrib><creatorcontrib>Aydt, Alexander P.</creatorcontrib><creatorcontrib>Zhang, Lichirui</creatorcontrib><creatorcontrib>Sergeyev, Ivan</creatorcontrib><creatorcontrib>Keeler, Eric G.</creatorcontrib><creatorcontrib>Choi, Bonnie</creatorcontrib><creatorcontrib>He, Shoushou</creatorcontrib><creatorcontrib>Reichman, David R.</creatorcontrib><creatorcontrib>Friesner, Richard A.</creatorcontrib><creatorcontrib>Nuckolls, Colin</creatorcontrib><creatorcontrib>Steigerwald, Michael L.</creatorcontrib><creatorcontrib>Roy, Xavier</creatorcontrib><creatorcontrib>McDermott, Ann E.</creatorcontrib><title>Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms</title><title>Chemphyschem</title><addtitle>Chemphyschem</addtitle><description>Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6Se8(PEt3)6. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6Se8] core while ligands function as an insulated shell. 59Co SSNMR measurements on the core and 31P, 13C on the ligands show that the neutral Co6Se8(PEt3)6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6Se8(PEt3)6]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.
Multinuclear NMR and quantum calculation reveal the atom‐like feature of a metal chalcogenide cluster, a superatom as the valence electrons/spins delocalize over the entire inorganic core and are insulated by its ligand shell.</description><subject>Aromaticity</subject><subject>cluster aromaticity</subject><subject>Diamagnetism</subject><subject>Electron spin</subject><subject>Electronic structure</subject><subject>Ligands</subject><subject>Magnetic properties</subject><subject>Molecular clusters</subject><subject>Molecular orbitals</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Paramagnetism</subject><subject>quantum calculations</subject><subject>spin/electron delocalization</subject><subject>SSNMR</subject><subject>superatomic solid</subject><issn>1439-4235</issn><issn>1439-7641</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNqF0M1LwzAYBvAgis7p1aMMvCiyLW--mhy1zg8QHExPIiFLE-zo2tq0iP71RjYnePH0hpdfHl4ehI4AjwBjMrb1qx0RTCjGWLAt1ANG1TARDLbXb0Yo30P7ISwikTiBXbRHJeYJMNZDl5PC2bapyoEps8GszsvBlSsqa4r807R53MfNc1qJmZOn00lLz8QLHp_DYNbVrjFttQwHaMebIrjD9eyjp-vJY3o7vH-4uUsv7oeWAmFDzwQnGBgk4I2fUydp5qSS3PhEYsUcESwjcwBuhZdOKEISlXHljZSe24z20ekqt26qt86FVi_zYF1RmNJVXdBEKkUTxjFEevKHLqquKeN1miiIQnAQUY1WyjZVCI3zum7ypWk-NGD93a7-bldv2o0fjtex3Xzpsg3_qTMCtQLveeE-_onT6fQ2_Q3_AiJKgjs</recordid><startdate>20240115</startdate><enddate>20240115</enddate><creator>Xu, Yunyao</creator><creator>Chen, Jia</creator><creator>Aydt, Alexander P.</creator><creator>Zhang, Lichirui</creator><creator>Sergeyev, Ivan</creator><creator>Keeler, Eric G.</creator><creator>Choi, Bonnie</creator><creator>He, Shoushou</creator><creator>Reichman, David R.</creator><creator>Friesner, Richard A.</creator><creator>Nuckolls, Colin</creator><creator>Steigerwald, Michael L.</creator><creator>Roy, Xavier</creator><creator>McDermott, Ann E.</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-9249-1649</orcidid><orcidid>https://orcid.org/0000-0001-5587-4854</orcidid><orcidid>https://orcid.org/0000-0002-0384-5493</orcidid><orcidid>https://orcid.org/0000-0001-6587-9528</orcidid><orcidid>https://orcid.org/0000-0002-5265-5637</orcidid><orcidid>https://orcid.org/0000-0002-8850-0725</orcidid><orcidid>https://orcid.org/0000-0002-9598-7148</orcidid></search><sort><creationdate>20240115</creationdate><title>Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms</title><author>Xu, Yunyao ; Chen, Jia ; Aydt, Alexander P. ; Zhang, Lichirui ; Sergeyev, Ivan ; Keeler, Eric G. ; Choi, Bonnie ; He, Shoushou ; Reichman, David R. ; Friesner, Richard A. ; Nuckolls, Colin ; Steigerwald, Michael L. ; Roy, Xavier ; McDermott, Ann E.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3124-f4652014171fafb3e83de8985af78094e264d2b115c6f8e692279d59fa88f5cd3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Aromaticity</topic><topic>cluster aromaticity</topic><topic>Diamagnetism</topic><topic>Electron spin</topic><topic>Electronic structure</topic><topic>Ligands</topic><topic>Magnetic properties</topic><topic>Molecular clusters</topic><topic>Molecular orbitals</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Paramagnetism</topic><topic>quantum calculations</topic><topic>spin/electron delocalization</topic><topic>SSNMR</topic><topic>superatomic solid</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Xu, Yunyao</creatorcontrib><creatorcontrib>Chen, Jia</creatorcontrib><creatorcontrib>Aydt, Alexander P.</creatorcontrib><creatorcontrib>Zhang, Lichirui</creatorcontrib><creatorcontrib>Sergeyev, Ivan</creatorcontrib><creatorcontrib>Keeler, Eric G.</creatorcontrib><creatorcontrib>Choi, Bonnie</creatorcontrib><creatorcontrib>He, Shoushou</creatorcontrib><creatorcontrib>Reichman, David R.</creatorcontrib><creatorcontrib>Friesner, Richard A.</creatorcontrib><creatorcontrib>Nuckolls, Colin</creatorcontrib><creatorcontrib>Steigerwald, Michael L.</creatorcontrib><creatorcontrib>Roy, Xavier</creatorcontrib><creatorcontrib>McDermott, Ann E.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemphyschem</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Xu, Yunyao</au><au>Chen, Jia</au><au>Aydt, Alexander P.</au><au>Zhang, Lichirui</au><au>Sergeyev, Ivan</au><au>Keeler, Eric G.</au><au>Choi, Bonnie</au><au>He, Shoushou</au><au>Reichman, David R.</au><au>Friesner, Richard A.</au><au>Nuckolls, Colin</au><au>Steigerwald, Michael L.</au><au>Roy, Xavier</au><au>McDermott, Ann E.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms</atitle><jtitle>Chemphyschem</jtitle><addtitle>Chemphyschem</addtitle><date>2024-01-15</date><risdate>2024</risdate><volume>25</volume><issue>2</issue><spage>e202300064</spage><epage>n/a</epage><pages>e202300064-n/a</pages><issn>1439-4235</issn><eissn>1439-7641</eissn><abstract>Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6Se8(PEt3)6. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6Se8] core while ligands function as an insulated shell. 59Co SSNMR measurements on the core and 31P, 13C on the ligands show that the neutral Co6Se8(PEt3)6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6Se8(PEt3)6]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.
Multinuclear NMR and quantum calculation reveal the atom‐like feature of a metal chalcogenide cluster, a superatom as the valence electrons/spins delocalize over the entire inorganic core and are insulated by its ligand shell.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>38057144</pmid><doi>10.1002/cphc.202300064</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-9249-1649</orcidid><orcidid>https://orcid.org/0000-0001-5587-4854</orcidid><orcidid>https://orcid.org/0000-0002-0384-5493</orcidid><orcidid>https://orcid.org/0000-0001-6587-9528</orcidid><orcidid>https://orcid.org/0000-0002-5265-5637</orcidid><orcidid>https://orcid.org/0000-0002-8850-0725</orcidid><orcidid>https://orcid.org/0000-0002-9598-7148</orcidid></addata></record> |
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| subjects | Aromaticity cluster aromaticity Diamagnetism Electron spin Electronic structure Ligands Magnetic properties Molecular clusters Molecular orbitals NMR Nuclear magnetic resonance Paramagnetism quantum calculations spin/electron delocalization SSNMR superatomic solid |
| title | Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms |
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