Impact of non-equilibrium molecular packings on singlet fission in microcrystals observed using 2D white-light microscopy
Singlet fission, the process of splitting a singlet exciton into two triplet excitons, has been proposed as a mechanism for improving the efficiency of future photovoltaic devices. In organic semiconductors exhibiting singlet fission, the geometric relationship between molecules plays an important r...
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| Veröffentlicht in: | Nature chemistry 2020-01, Vol.12 (1), p.40-47 |
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| creator | Jones, Andrew C. Kearns, Nicholas M. Ho, Jia-Jung Flach, Jessica T. Zanni, Martin T. |
| description | Singlet fission, the process of splitting a singlet exciton into two triplet excitons, has been proposed as a mechanism for improving the efficiency of future photovoltaic devices. In organic semiconductors exhibiting singlet fission, the geometric relationship between molecules plays an important role by setting the intermolecular couplings that determine the system energetics. Here, we spatially image TIPS-pentacene microcrystals using ultrafast two-dimensional white-light microscopy and discover a low-energy singlet state sparsely distributed throughout the microcrystals, with higher concentrations at edges and morphological defects. The spectra of these singlet states are consistent with slip-stacked molecular geometries and increased charge-transfer couplings. The picosecond-timescale kinetics of these low-energy singlet states matches that of the correlated triplet-pair state, which we attribute to singlet/triplet-pair interconversion at these sites. Our observations support the conclusion that small populations of geometries with favourable energetics can play outsized roles in singlet fission processes.
Intermolecular coupling plays a critical role in singlet fission. Now, high-resolution 2D white-light spectroscopy has been used to map the presence of non-equilibrium molecular packing in single TIPS-pentacene microcrystals and characterize its effect on the dynamics of singlet fission. |
| doi_str_mv | 10.1038/s41557-019-0368-9 |
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Intermolecular coupling plays a critical role in singlet fission. Now, high-resolution 2D white-light spectroscopy has been used to map the presence of non-equilibrium molecular packing in single TIPS-pentacene microcrystals and characterize its effect on the dynamics of singlet fission.</description><identifier>ISSN: 1755-4330</identifier><identifier>EISSN: 1755-4349</identifier><identifier>DOI: 10.1038/s41557-019-0368-9</identifier><identifier>PMID: 31792384</identifier><language>eng</language><publisher>London: Nature Publishing Group UK</publisher><subject>639/638/439/946 ; 639/638/440/527 ; 639/638/675 ; Analytical Chemistry ; Biochemistry ; Charge transfer ; Chemistry ; Chemistry and Materials Science ; Chemistry/Food Science ; Coupling (molecular) ; Couplings ; Excitons ; Fission ; Inorganic Chemistry ; Light microscopy ; Microcrystals ; Microscopy ; Optical microscopy ; Organic Chemistry ; Organic semiconductors ; Photovoltaic cells ; Photovoltaics ; Physical Chemistry ; White light</subject><ispartof>Nature chemistry, 2020-01, Vol.12 (1), p.40-47</ispartof><rights>The Author(s), under exclusive licence to Springer Nature Limited 2019</rights><rights>Copyright Nature Publishing Group Jan 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c475t-de437b57e99fe24c704b6ebfee3d3a4cc01cc1e10dd37c999ef18c61731e75c63</citedby><cites>FETCH-LOGICAL-c475t-de437b57e99fe24c704b6ebfee3d3a4cc01cc1e10dd37c999ef18c61731e75c63</cites><orcidid>0000-0002-9767-8082</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1038/s41557-019-0368-9$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1038/s41557-019-0368-9$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31792384$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Jones, Andrew C.</creatorcontrib><creatorcontrib>Kearns, Nicholas M.</creatorcontrib><creatorcontrib>Ho, Jia-Jung</creatorcontrib><creatorcontrib>Flach, Jessica T.</creatorcontrib><creatorcontrib>Zanni, Martin T.</creatorcontrib><title>Impact of non-equilibrium molecular packings on singlet fission in microcrystals observed using 2D white-light microscopy</title><title>Nature chemistry</title><addtitle>Nat. Chem</addtitle><addtitle>Nat Chem</addtitle><description>Singlet fission, the process of splitting a singlet exciton into two triplet excitons, has been proposed as a mechanism for improving the efficiency of future photovoltaic devices. In organic semiconductors exhibiting singlet fission, the geometric relationship between molecules plays an important role by setting the intermolecular couplings that determine the system energetics. Here, we spatially image TIPS-pentacene microcrystals using ultrafast two-dimensional white-light microscopy and discover a low-energy singlet state sparsely distributed throughout the microcrystals, with higher concentrations at edges and morphological defects. The spectra of these singlet states are consistent with slip-stacked molecular geometries and increased charge-transfer couplings. The picosecond-timescale kinetics of these low-energy singlet states matches that of the correlated triplet-pair state, which we attribute to singlet/triplet-pair interconversion at these sites. Our observations support the conclusion that small populations of geometries with favourable energetics can play outsized roles in singlet fission processes.
Intermolecular coupling plays a critical role in singlet fission. 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Kearns, Nicholas M. ; Ho, Jia-Jung ; Flach, Jessica T. ; Zanni, Martin T.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c475t-de437b57e99fe24c704b6ebfee3d3a4cc01cc1e10dd37c999ef18c61731e75c63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>639/638/439/946</topic><topic>639/638/440/527</topic><topic>639/638/675</topic><topic>Analytical Chemistry</topic><topic>Biochemistry</topic><topic>Charge transfer</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chemistry/Food Science</topic><topic>Coupling (molecular)</topic><topic>Couplings</topic><topic>Excitons</topic><topic>Fission</topic><topic>Inorganic Chemistry</topic><topic>Light microscopy</topic><topic>Microcrystals</topic><topic>Microscopy</topic><topic>Optical microscopy</topic><topic>Organic Chemistry</topic><topic>Organic semiconductors</topic><topic>Photovoltaic cells</topic><topic>Photovoltaics</topic><topic>Physical Chemistry</topic><topic>White light</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Jones, Andrew C.</creatorcontrib><creatorcontrib>Kearns, Nicholas M.</creatorcontrib><creatorcontrib>Ho, Jia-Jung</creatorcontrib><creatorcontrib>Flach, Jessica T.</creatorcontrib><creatorcontrib>Zanni, Martin T.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Chemoreception Abstracts</collection><collection>Health & Medical Collection</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Medical Database (Alumni Edition)</collection><collection>ProQuest Pharma Collection</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Natural Science Collection</collection><collection>Hospital Premium Collection</collection><collection>Hospital Premium Collection (Alumni Edition)</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest One Sustainability</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>Biological Science Collection</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>Engineering Research Database</collection><collection>Health Research Premium Collection</collection><collection>Health Research Premium Collection (Alumni)</collection><collection>ProQuest Central Student</collection><collection>SciTech Premium Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Materials Science Database</collection><collection>ProQuest Biological Science Collection</collection><collection>Health & Medical Collection (Alumni Edition)</collection><collection>Medical Database</collection><collection>Biological Science Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>MEDLINE - Academic</collection><jtitle>Nature chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Jones, Andrew C.</au><au>Kearns, Nicholas M.</au><au>Ho, Jia-Jung</au><au>Flach, Jessica T.</au><au>Zanni, Martin T.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Impact of non-equilibrium molecular packings on singlet fission in microcrystals observed using 2D white-light microscopy</atitle><jtitle>Nature chemistry</jtitle><stitle>Nat. Chem</stitle><addtitle>Nat Chem</addtitle><date>2020-01-01</date><risdate>2020</risdate><volume>12</volume><issue>1</issue><spage>40</spage><epage>47</epage><pages>40-47</pages><issn>1755-4330</issn><eissn>1755-4349</eissn><abstract>Singlet fission, the process of splitting a singlet exciton into two triplet excitons, has been proposed as a mechanism for improving the efficiency of future photovoltaic devices. In organic semiconductors exhibiting singlet fission, the geometric relationship between molecules plays an important role by setting the intermolecular couplings that determine the system energetics. Here, we spatially image TIPS-pentacene microcrystals using ultrafast two-dimensional white-light microscopy and discover a low-energy singlet state sparsely distributed throughout the microcrystals, with higher concentrations at edges and morphological defects. The spectra of these singlet states are consistent with slip-stacked molecular geometries and increased charge-transfer couplings. The picosecond-timescale kinetics of these low-energy singlet states matches that of the correlated triplet-pair state, which we attribute to singlet/triplet-pair interconversion at these sites. Our observations support the conclusion that small populations of geometries with favourable energetics can play outsized roles in singlet fission processes.
Intermolecular coupling plays a critical role in singlet fission. Now, high-resolution 2D white-light spectroscopy has been used to map the presence of non-equilibrium molecular packing in single TIPS-pentacene microcrystals and characterize its effect on the dynamics of singlet fission.</abstract><cop>London</cop><pub>Nature Publishing Group UK</pub><pmid>31792384</pmid><doi>10.1038/s41557-019-0368-9</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-9767-8082</orcidid></addata></record> |
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| subjects | 639/638/439/946 639/638/440/527 639/638/675 Analytical Chemistry Biochemistry Charge transfer Chemistry Chemistry and Materials Science Chemistry/Food Science Coupling (molecular) Couplings Excitons Fission Inorganic Chemistry Light microscopy Microcrystals Microscopy Optical microscopy Organic Chemistry Organic semiconductors Photovoltaic cells Photovoltaics Physical Chemistry White light |
| title | Impact of non-equilibrium molecular packings on singlet fission in microcrystals observed using 2D white-light microscopy |
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