Enhanced intersystem crossing in core-twisted aromatics
We describe the design, bottom-up synthesis and X-ray single crystal structure of systematically twisted aromatics and for efficient intersystem crossing. Steric congestion at the cove region creates a nonplanar geometry that induces a significant yield of triplet excited states in the electron-poor...
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Veröffentlicht in: | Chemical science (Cambridge) 2017-03, Vol.8 (3), p.1776-1782 |
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creator | Nagarajan, Kalaivanan Mallia, Ajith R Muraleedharan, Keerthi Hariharan, Mahesh |
description | We describe the design, bottom-up synthesis and X-ray single crystal structure of systematically twisted aromatics
and
for efficient intersystem crossing. Steric congestion at the cove region creates a nonplanar geometry that induces a significant yield of triplet excited states in the electron-poor core-twisted aromatics
and
. A systematic increase in the number of twisted regions in
and
results in a concomitant enhancement in the rate and yield of intersystem crossing, monitored using femtosecond and nanosecond transient absorption spectroscopy. Time-resolved absorption spectroscopic measurements display enhanced triplet quantum yields (
= 10 ± 1% for
and
= 30 ± 2% for
) in the twisted aromatics when compared to a negligible
( |
doi_str_mv | 10.1039/c6sc05126j |
format | Article |
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and
for efficient intersystem crossing. Steric congestion at the cove region creates a nonplanar geometry that induces a significant yield of triplet excited states in the electron-poor core-twisted aromatics
and
. A systematic increase in the number of twisted regions in
and
results in a concomitant enhancement in the rate and yield of intersystem crossing, monitored using femtosecond and nanosecond transient absorption spectroscopy. Time-resolved absorption spectroscopic measurements display enhanced triplet quantum yields (
= 10 ± 1% for
and
= 30 ± 2% for
) in the twisted aromatics when compared to a negligible
(<1%) in the planar analog
. Twist-induced spin-orbit coupling
activated out-of-plane C-H/C[double bond, length as m-dash]C vibrations can facilitate the formation of triplet excited states in twisted aromatics
and
, in contrast to the negligible intersystem crossing in the planar analog
. The ease of synthesis, high solubility, access to triplet excited states and strong electron affinity make such imide functionalized core-twisted aromatics desirable materials for organic electronics such as solar cells.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c6sc05126j</identifier><identifier>PMID: 28694952</identifier><language>eng</language><publisher>England</publisher><subject>Absorption spectroscopy ; Affinity ; Electronics ; Femtosecond ; Nanostructure ; Solar cells ; Spin-orbit interactions ; Vibration</subject><ispartof>Chemical science (Cambridge), 2017-03, Vol.8 (3), p.1776-1782</ispartof><rights>This journal is © The Royal Society of Chemistry 2017.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c463t-4b0ece07a64415a20e616556a13968d0bcf0cc40d792e4dc1ebc59bb111879c03</citedby><cites>FETCH-LOGICAL-c463t-4b0ece07a64415a20e616556a13968d0bcf0cc40d792e4dc1ebc59bb111879c03</cites><orcidid>0000-0002-3237-6235</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,865,27926,27927</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28694952$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Nagarajan, Kalaivanan</creatorcontrib><creatorcontrib>Mallia, Ajith R</creatorcontrib><creatorcontrib>Muraleedharan, Keerthi</creatorcontrib><creatorcontrib>Hariharan, Mahesh</creatorcontrib><title>Enhanced intersystem crossing in core-twisted aromatics</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>We describe the design, bottom-up synthesis and X-ray single crystal structure of systematically twisted aromatics
and
for efficient intersystem crossing. Steric congestion at the cove region creates a nonplanar geometry that induces a significant yield of triplet excited states in the electron-poor core-twisted aromatics
and
. A systematic increase in the number of twisted regions in
and
results in a concomitant enhancement in the rate and yield of intersystem crossing, monitored using femtosecond and nanosecond transient absorption spectroscopy. Time-resolved absorption spectroscopic measurements display enhanced triplet quantum yields (
= 10 ± 1% for
and
= 30 ± 2% for
) in the twisted aromatics when compared to a negligible
(<1%) in the planar analog
. Twist-induced spin-orbit coupling
activated out-of-plane C-H/C[double bond, length as m-dash]C vibrations can facilitate the formation of triplet excited states in twisted aromatics
and
, in contrast to the negligible intersystem crossing in the planar analog
. The ease of synthesis, high solubility, access to triplet excited states and strong electron affinity make such imide functionalized core-twisted aromatics desirable materials for organic electronics such as solar cells.</description><subject>Absorption spectroscopy</subject><subject>Affinity</subject><subject>Electronics</subject><subject>Femtosecond</subject><subject>Nanostructure</subject><subject>Solar cells</subject><subject>Spin-orbit interactions</subject><subject>Vibration</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNqFkE1Lw0AQhhdRbKm9-AMkRxGiM_uZPUqoXxQ8qOewmWw1pUnqbor03xtr7dWBYV5mHl6Yl7FzhGsEYW9IRwKFXC-P2JiDxFQrYY8PmsOITWNcwlBCoOLmlI14pq20io-ZmbUfriVfJXXb-xC3sfdNQqGLsW7fh2VCXfBp_1UPhypxoWtcX1M8YycLt4p-up8T9nY3e80f0vnz_WN-O09JatGnsgRPHozTUqJyHLxGrZR2KKzOKihpAUQSKmO5lxWhL0nZskTEzFgCMWGXv77r0H1ufOyLpo7kVyvX-m4TC7RorBYG7P9olknkIht6wq5-0d2jwS-KdagbF7YFQvETa5Hrl3wX69MAX-x9N2XjqwP6F6L4BpRHcSY</recordid><startdate>20170301</startdate><enddate>20170301</enddate><creator>Nagarajan, Kalaivanan</creator><creator>Mallia, Ajith R</creator><creator>Muraleedharan, Keerthi</creator><creator>Hariharan, Mahesh</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-3237-6235</orcidid></search><sort><creationdate>20170301</creationdate><title>Enhanced intersystem crossing in core-twisted aromatics</title><author>Nagarajan, Kalaivanan ; Mallia, Ajith R ; Muraleedharan, Keerthi ; Hariharan, Mahesh</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c463t-4b0ece07a64415a20e616556a13968d0bcf0cc40d792e4dc1ebc59bb111879c03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Absorption spectroscopy</topic><topic>Affinity</topic><topic>Electronics</topic><topic>Femtosecond</topic><topic>Nanostructure</topic><topic>Solar cells</topic><topic>Spin-orbit interactions</topic><topic>Vibration</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Nagarajan, Kalaivanan</creatorcontrib><creatorcontrib>Mallia, Ajith R</creatorcontrib><creatorcontrib>Muraleedharan, Keerthi</creatorcontrib><creatorcontrib>Hariharan, Mahesh</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Nagarajan, Kalaivanan</au><au>Mallia, Ajith R</au><au>Muraleedharan, Keerthi</au><au>Hariharan, Mahesh</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Enhanced intersystem crossing in core-twisted aromatics</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2017-03-01</date><risdate>2017</risdate><volume>8</volume><issue>3</issue><spage>1776</spage><epage>1782</epage><pages>1776-1782</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>We describe the design, bottom-up synthesis and X-ray single crystal structure of systematically twisted aromatics
and
for efficient intersystem crossing. Steric congestion at the cove region creates a nonplanar geometry that induces a significant yield of triplet excited states in the electron-poor core-twisted aromatics
and
. A systematic increase in the number of twisted regions in
and
results in a concomitant enhancement in the rate and yield of intersystem crossing, monitored using femtosecond and nanosecond transient absorption spectroscopy. Time-resolved absorption spectroscopic measurements display enhanced triplet quantum yields (
= 10 ± 1% for
and
= 30 ± 2% for
) in the twisted aromatics when compared to a negligible
(<1%) in the planar analog
. Twist-induced spin-orbit coupling
activated out-of-plane C-H/C[double bond, length as m-dash]C vibrations can facilitate the formation of triplet excited states in twisted aromatics
and
, in contrast to the negligible intersystem crossing in the planar analog
. The ease of synthesis, high solubility, access to triplet excited states and strong electron affinity make such imide functionalized core-twisted aromatics desirable materials for organic electronics such as solar cells.</abstract><cop>England</cop><pmid>28694952</pmid><doi>10.1039/c6sc05126j</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-3237-6235</orcidid><oa>free_for_read</oa></addata></record> |
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language | eng |
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source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
subjects | Absorption spectroscopy Affinity Electronics Femtosecond Nanostructure Solar cells Spin-orbit interactions Vibration |
title | Enhanced intersystem crossing in core-twisted aromatics |
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