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Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence
In a previous investigation, it was shown that [Cu(tpym)(PPh 3 )]PF 6 1 with tpym = tris(2-pyridyl)methane represents a deep blue emitter ( λ max = 466 nm) though with a low emission quantum yield Φ PL if doped in a polymer (7%) or dissolved in a fluid solvent (
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2018-12, Vol.47 (47), p.1767-1776 |
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| cites | cdi_FETCH-LOGICAL-c403t-694d248d56369869f9900b156f7f80b5fcdb847a953068427ce49feaebaf82b33 |
| container_end_page | 1776 |
| container_issue | 47 |
| container_start_page | 1767 |
| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | 47 |
| creator | Schinabeck, Alexander Rau, Nicholas Klein, Marius Sundermeyer, Jörg Yersin, Hartmut |
| description | In a previous investigation, it was shown that [Cu(tpym)(PPh
3
)]PF
6
1
with tpym = tris(2-pyridyl)methane represents a deep blue emitter (
λ
max
= 466 nm) though with a low emission quantum yield
Φ
PL
if doped in a polymer (7%) or dissolved in a fluid solvent ( |
| doi_str_mv | 10.1039/c8dt04093a |
| format | article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmed_primary_30465052</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2149844689</sourcerecordid><originalsourceid>FETCH-LOGICAL-c403t-694d248d56369869f9900b156f7f80b5fcdb847a953068427ce49feaebaf82b33</originalsourceid><addsrcrecordid>eNpd0c1rHCEYBnAJLflqL7m3CL0khUkddRw9LrtJWgj0sj0PjvO6a5gZJ-q0zX8ft5tsIQfxBX88vPggdFGS65Iw9c3ILhFOFNNH6LTkdV0oyvi7w0zFCTqL8YEQSklFj9EJI1xUeTxFv1cAE277GTAMLiU3bvByvrzCKbjJd9j4YerhL8RrvILoNiP2Fm_dZosfZz2mecBPDvoODzpBcLqPOG79n13KerG6LXSMLibo8LT1MZ8A0cBo4AN6bzOGjy_3Ofp1e7Nefi_uf979WC7uC8MJS4VQvKNcdpVgQkmhrFKEtGUlbG0laStrulbyWquKESE5rQ1wZUFDq62kLWPn6HKfOwX_OENMzeDyBn2vR_BzbGjJleRcSJXplzf0wc9hzNvtlFQlpZJm9XWvTPAxBrDNFNygw1NTkmbXRrOUq_W_NhYZf36JnNsBugN9_f4MPu1BiObw-r9O9gwvno6M</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2148912282</pqid></control><display><type>article</type><title>Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence</title><source>Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list)</source><creator>Schinabeck, Alexander ; Rau, Nicholas ; Klein, Marius ; Sundermeyer, Jörg ; Yersin, Hartmut</creator><creatorcontrib>Schinabeck, Alexander ; Rau, Nicholas ; Klein, Marius ; Sundermeyer, Jörg ; Yersin, Hartmut</creatorcontrib><description>In a previous investigation, it was shown that [Cu(tpym)(PPh
3
)]PF
6
1
with tpym = tris(2-pyridyl)methane represents a deep blue emitter (
λ
max
= 466 nm) though with a low emission quantum yield
Φ
PL
if doped in a polymer (7%) or dissolved in a fluid solvent (<1%). In this study, we present new tripod compounds with sterically demanding ligands: [Cu(tpym)(P(
o
-tol)
3
)]PF
6
2
and [Cu(tpym)(P(
o
-butyl-ph)
3
)]PF
6
3
with P(
o
-tol)
3
= tris(
ortho
-tolyl)phosphine and P(
o
-butyl-ph)
3
= tris(
ortho-n
-butylphenyl)phosphine. These compounds show high emission quantum yields even in a fluid solution (dichloromethane) reaching a benchmark value for
3
of
Φ
PL
= 76%. This becomes possible due to the specific design of rigidifying the complexes. Importantly, the deep blue emission color is maintained or even further blue shifted to
λ
max
= 452 nm (compound
3
powder). Compound
2
is characterized photophysically in detail. In particular, it is shown that the lowest excited triplet state T
1
experiences very efficient spin-orbit coupling (SOC). Accordingly, the phosphorescence decay rate is as large as 5 × 10
4
s
−1
(20 μs) belonging to the fastest T
1
→ S
0
transition values (shortest decay times) reported so far. Investigations down to
T
= 1.5 K reveal a large total zero-field splitting (ZFS) of 7 cm
−1
(0.9 meV). Although thermally activated delayed fluorescence (TADF) grows in at
T
≥ 160 K, the phosphorescence of
2
still dominates (60%) over TADF (40%) at ambient temperature. Thus, the compound represents a singlet harvesting-plus-triplet harvesting material, if applied in an OLED.
Triplet and singlet harvesting in combination with enhancing the emitter rigidity leads to a landmark value of the photoluminescence quantum yield for dissolved Cu(
i
) complexes.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c8dt04093a</identifier><identifier>PMID: 30465052</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Ambient temperature ; Atomic energy levels ; Copper ; Crystallography ; Decay rate ; Dichloromethane ; Emission ; Emitters ; Fluorescence ; Harvesting ; Organic light emitting diodes ; Phosphorescence ; Spin-orbit interactions</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2018-12, Vol.47 (47), p.1767-1776</ispartof><rights>Copyright Royal Society of Chemistry 2018</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c403t-694d248d56369869f9900b156f7f80b5fcdb847a953068427ce49feaebaf82b33</citedby><cites>FETCH-LOGICAL-c403t-694d248d56369869f9900b156f7f80b5fcdb847a953068427ce49feaebaf82b33</cites><orcidid>0000-0003-1039-7673 ; 0000-0001-8244-8201 ; 0000-0003-3216-1370</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30465052$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Schinabeck, Alexander</creatorcontrib><creatorcontrib>Rau, Nicholas</creatorcontrib><creatorcontrib>Klein, Marius</creatorcontrib><creatorcontrib>Sundermeyer, Jörg</creatorcontrib><creatorcontrib>Yersin, Hartmut</creatorcontrib><title>Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>In a previous investigation, it was shown that [Cu(tpym)(PPh
3
)]PF
6
1
with tpym = tris(2-pyridyl)methane represents a deep blue emitter (
λ
max
= 466 nm) though with a low emission quantum yield
Φ
PL
if doped in a polymer (7%) or dissolved in a fluid solvent (<1%). In this study, we present new tripod compounds with sterically demanding ligands: [Cu(tpym)(P(
o
-tol)
3
)]PF
6
2
and [Cu(tpym)(P(
o
-butyl-ph)
3
)]PF
6
3
with P(
o
-tol)
3
= tris(
ortho
-tolyl)phosphine and P(
o
-butyl-ph)
3
= tris(
ortho-n
-butylphenyl)phosphine. These compounds show high emission quantum yields even in a fluid solution (dichloromethane) reaching a benchmark value for
3
of
Φ
PL
= 76%. This becomes possible due to the specific design of rigidifying the complexes. Importantly, the deep blue emission color is maintained or even further blue shifted to
λ
max
= 452 nm (compound
3
powder). Compound
2
is characterized photophysically in detail. In particular, it is shown that the lowest excited triplet state T
1
experiences very efficient spin-orbit coupling (SOC). Accordingly, the phosphorescence decay rate is as large as 5 × 10
4
s
−1
(20 μs) belonging to the fastest T
1
→ S
0
transition values (shortest decay times) reported so far. Investigations down to
T
= 1.5 K reveal a large total zero-field splitting (ZFS) of 7 cm
−1
(0.9 meV). Although thermally activated delayed fluorescence (TADF) grows in at
T
≥ 160 K, the phosphorescence of
2
still dominates (60%) over TADF (40%) at ambient temperature. Thus, the compound represents a singlet harvesting-plus-triplet harvesting material, if applied in an OLED.
Triplet and singlet harvesting in combination with enhancing the emitter rigidity leads to a landmark value of the photoluminescence quantum yield for dissolved Cu(
i
) complexes.</description><subject>Ambient temperature</subject><subject>Atomic energy levels</subject><subject>Copper</subject><subject>Crystallography</subject><subject>Decay rate</subject><subject>Dichloromethane</subject><subject>Emission</subject><subject>Emitters</subject><subject>Fluorescence</subject><subject>Harvesting</subject><subject>Organic light emitting diodes</subject><subject>Phosphorescence</subject><subject>Spin-orbit interactions</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpd0c1rHCEYBnAJLflqL7m3CL0khUkddRw9LrtJWgj0sj0PjvO6a5gZJ-q0zX8ft5tsIQfxBX88vPggdFGS65Iw9c3ILhFOFNNH6LTkdV0oyvi7w0zFCTqL8YEQSklFj9EJI1xUeTxFv1cAE277GTAMLiU3bvByvrzCKbjJd9j4YerhL8RrvILoNiP2Fm_dZosfZz2mecBPDvoODzpBcLqPOG79n13KerG6LXSMLibo8LT1MZ8A0cBo4AN6bzOGjy_3Ofp1e7Nefi_uf979WC7uC8MJS4VQvKNcdpVgQkmhrFKEtGUlbG0laStrulbyWquKESE5rQ1wZUFDq62kLWPn6HKfOwX_OENMzeDyBn2vR_BzbGjJleRcSJXplzf0wc9hzNvtlFQlpZJm9XWvTPAxBrDNFNygw1NTkmbXRrOUq_W_NhYZf36JnNsBugN9_f4MPu1BiObw-r9O9gwvno6M</recordid><startdate>20181221</startdate><enddate>20181221</enddate><creator>Schinabeck, Alexander</creator><creator>Rau, Nicholas</creator><creator>Klein, Marius</creator><creator>Sundermeyer, Jörg</creator><creator>Yersin, Hartmut</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-1039-7673</orcidid><orcidid>https://orcid.org/0000-0001-8244-8201</orcidid><orcidid>https://orcid.org/0000-0003-3216-1370</orcidid></search><sort><creationdate>20181221</creationdate><title>Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence</title><author>Schinabeck, Alexander ; Rau, Nicholas ; Klein, Marius ; Sundermeyer, Jörg ; Yersin, Hartmut</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c403t-694d248d56369869f9900b156f7f80b5fcdb847a953068427ce49feaebaf82b33</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Ambient temperature</topic><topic>Atomic energy levels</topic><topic>Copper</topic><topic>Crystallography</topic><topic>Decay rate</topic><topic>Dichloromethane</topic><topic>Emission</topic><topic>Emitters</topic><topic>Fluorescence</topic><topic>Harvesting</topic><topic>Organic light emitting diodes</topic><topic>Phosphorescence</topic><topic>Spin-orbit interactions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Schinabeck, Alexander</creatorcontrib><creatorcontrib>Rau, Nicholas</creatorcontrib><creatorcontrib>Klein, Marius</creatorcontrib><creatorcontrib>Sundermeyer, Jörg</creatorcontrib><creatorcontrib>Yersin, Hartmut</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Schinabeck, Alexander</au><au>Rau, Nicholas</au><au>Klein, Marius</au><au>Sundermeyer, Jörg</au><au>Yersin, Hartmut</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2018-12-21</date><risdate>2018</risdate><volume>47</volume><issue>47</issue><spage>1767</spage><epage>1776</epage><pages>1767-1776</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>In a previous investigation, it was shown that [Cu(tpym)(PPh
3
)]PF
6
1
with tpym = tris(2-pyridyl)methane represents a deep blue emitter (
λ
max
= 466 nm) though with a low emission quantum yield
Φ
PL
if doped in a polymer (7%) or dissolved in a fluid solvent (<1%). In this study, we present new tripod compounds with sterically demanding ligands: [Cu(tpym)(P(
o
-tol)
3
)]PF
6
2
and [Cu(tpym)(P(
o
-butyl-ph)
3
)]PF
6
3
with P(
o
-tol)
3
= tris(
ortho
-tolyl)phosphine and P(
o
-butyl-ph)
3
= tris(
ortho-n
-butylphenyl)phosphine. These compounds show high emission quantum yields even in a fluid solution (dichloromethane) reaching a benchmark value for
3
of
Φ
PL
= 76%. This becomes possible due to the specific design of rigidifying the complexes. Importantly, the deep blue emission color is maintained or even further blue shifted to
λ
max
= 452 nm (compound
3
powder). Compound
2
is characterized photophysically in detail. In particular, it is shown that the lowest excited triplet state T
1
experiences very efficient spin-orbit coupling (SOC). Accordingly, the phosphorescence decay rate is as large as 5 × 10
4
s
−1
(20 μs) belonging to the fastest T
1
→ S
0
transition values (shortest decay times) reported so far. Investigations down to
T
= 1.5 K reveal a large total zero-field splitting (ZFS) of 7 cm
−1
(0.9 meV). Although thermally activated delayed fluorescence (TADF) grows in at
T
≥ 160 K, the phosphorescence of
2
still dominates (60%) over TADF (40%) at ambient temperature. Thus, the compound represents a singlet harvesting-plus-triplet harvesting material, if applied in an OLED.
Triplet and singlet harvesting in combination with enhancing the emitter rigidity leads to a landmark value of the photoluminescence quantum yield for dissolved Cu(
i
) complexes.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>30465052</pmid><doi>10.1039/c8dt04093a</doi><tpages>1</tpages><orcidid>https://orcid.org/0000-0003-1039-7673</orcidid><orcidid>https://orcid.org/0000-0001-8244-8201</orcidid><orcidid>https://orcid.org/0000-0003-3216-1370</orcidid></addata></record> |
| fulltext | fulltext |
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| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2018-12, Vol.47 (47), p.1767-1776 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_pubmed_primary_30465052 |
| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| subjects | Ambient temperature Atomic energy levels Copper Crystallography Decay rate Dichloromethane Emission Emitters Fluorescence Harvesting Organic light emitting diodes Phosphorescence Spin-orbit interactions |
| title | Deep blue emitting Cu() tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence |
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