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Article: Emissive or nonemissive? a theoretical analysis of the phosphorescence efficiencies of cyclometalated platinum(II) complexes
Title | Emissive or nonemissive? a theoretical analysis of the phosphorescence efficiencies of cyclometalated platinum(II) complexes |
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Authors | |
Keywords | Density functional calculations Electronic structure Jahn-teller distortion Platinum Spin-orbit coupling |
Issue Date | 2009 |
Publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry |
Citation | Chemistry - A European Journal, 2009, v. 15 n. 29, p. 7225-7237 How to Cite? |
Abstract | We herein report a theoretical analysis based on a density functional theory/time-dependent density functional theory (DFT/TDDFT) approach to understand the different phosphorescence efficiencies of a family of cyclometalated platinum(II) complexes: [Pt(NCN)Cl] (1; NCN = l,3-bis(2-pyridyl)phenyl -), [Pt-(CNN)Cl] (2; CNN=6-phenyl-2,2′- bipyridyl -), [Pt(CNC)(CNPh)] (3; CNC = 2,6-diphenylpyridyl 2-), [Pt(RCNN)Cl] (4; R-CNN = 3-(6′-(2″-naphthyl)- 2′-pyridyl)isoquinolinyl -), and [Pt(R-CNC)(CNPh)] (5; R-CNC=2,6bis(2′-naphthyl)pyridyl 2-). By considering both the spin-orbit coupling (SOC) and the electronic structures of these complexes at their respective optimized singlet ground (S 0) and first triplet (T opt 1 ,) excited states, we were able to rationalize the experimental findings that 1 ) 1 is a strong emitter while its isomer 2 is only weakly emissive in CH 2Cl 2 solution at room temperature; 2) although the cyclometalated ligand of 3 has a higher ligand-field strength than that of 1, 3 is nonemissive in CH 2Cl 2 solution at 298 K; and 3) extension of π conjugation at the lateral aryl rings of the cyclometalated ligands of 2 and 3 to give 4 and 5, respectively, leads to increased emission quantum yields under the same conditions. We found that Jahn-Teller and pseudoJahn-Teller effects are operative in complexes 2 and 3, respectively, on going from the optimized S 0 ground state to the optimized T opt 1, excited state, and thus lead to large excitedstate structural distortions and hence fast nonradiative decay. Furthermore, a strong-field ligand may push the two different occupied d orbitais so far apart that the SOC effect is small and the radiative decay rate is slow. This work is an example of electronic-structure-driven tuning of the phosphorescence efficiency, and the DFT/TDDFT approach is demonstrated to be a versatile tool for the design of phosphorescent materials with target characteristics. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA. |
Persistent Identifier | http://hdl.handle.net/10722/70469 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Tong, GSM | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2010-09-06T06:23:10Z | - |
dc.date.available | 2010-09-06T06:23:10Z | - |
dc.date.issued | 2009 | en_HK |
dc.identifier.citation | Chemistry - A European Journal, 2009, v. 15 n. 29, p. 7225-7237 | en_HK |
dc.identifier.issn | 0947-6539 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/70469 | - |
dc.description.abstract | We herein report a theoretical analysis based on a density functional theory/time-dependent density functional theory (DFT/TDDFT) approach to understand the different phosphorescence efficiencies of a family of cyclometalated platinum(II) complexes: [Pt(NCN)Cl] (1; NCN = l,3-bis(2-pyridyl)phenyl -), [Pt-(CNN)Cl] (2; CNN=6-phenyl-2,2′- bipyridyl -), [Pt(CNC)(CNPh)] (3; CNC = 2,6-diphenylpyridyl 2-), [Pt(RCNN)Cl] (4; R-CNN = 3-(6′-(2″-naphthyl)- 2′-pyridyl)isoquinolinyl -), and [Pt(R-CNC)(CNPh)] (5; R-CNC=2,6bis(2′-naphthyl)pyridyl 2-). By considering both the spin-orbit coupling (SOC) and the electronic structures of these complexes at their respective optimized singlet ground (S 0) and first triplet (T opt 1 ,) excited states, we were able to rationalize the experimental findings that 1 ) 1 is a strong emitter while its isomer 2 is only weakly emissive in CH 2Cl 2 solution at room temperature; 2) although the cyclometalated ligand of 3 has a higher ligand-field strength than that of 1, 3 is nonemissive in CH 2Cl 2 solution at 298 K; and 3) extension of π conjugation at the lateral aryl rings of the cyclometalated ligands of 2 and 3 to give 4 and 5, respectively, leads to increased emission quantum yields under the same conditions. We found that Jahn-Teller and pseudoJahn-Teller effects are operative in complexes 2 and 3, respectively, on going from the optimized S 0 ground state to the optimized T opt 1, excited state, and thus lead to large excitedstate structural distortions and hence fast nonradiative decay. Furthermore, a strong-field ligand may push the two different occupied d orbitais so far apart that the SOC effect is small and the radiative decay rate is slow. This work is an example of electronic-structure-driven tuning of the phosphorescence efficiency, and the DFT/TDDFT approach is demonstrated to be a versatile tool for the design of phosphorescent materials with target characteristics. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA. | en_HK |
dc.language | eng | en_HK |
dc.publisher | Wiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry | en_HK |
dc.relation.ispartof | Chemistry - A European Journal | en_HK |
dc.subject | Density functional calculations | en_HK |
dc.subject | Electronic structure | en_HK |
dc.subject | Jahn-teller distortion | en_HK |
dc.subject | Platinum | en_HK |
dc.subject | Spin-orbit coupling | en_HK |
dc.title | Emissive or nonemissive? a theoretical analysis of the phosphorescence efficiencies of cyclometalated platinum(II) complexes | en_HK |
dc.type | Article | en_HK |
dc.identifier.openurl | http://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=15&spage=7225&epage=7237&date=2009&atitle=Emissive+or+Nonemissive?+A+Theoretical+Analysis+of+the+Phosphorescence+Efficiencies+of+Cyclometalated+Platinum(II)+Complexes | en_HK |
dc.identifier.email | Tong, GSM:tongsm@hkucc.hku.hk | en_HK |
dc.identifier.email | Che, CM:cmche@hku.hk | en_HK |
dc.identifier.authority | Tong, GSM=rp00790 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1002/chem.200802485 | en_HK |
dc.identifier.pmid | 19544517 | - |
dc.identifier.scopus | eid_2-s2.0-67650581269 | en_HK |
dc.identifier.hkuros | 167107 | en_HK |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-67650581269&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 15 | en_HK |
dc.identifier.issue | 29 | en_HK |
dc.identifier.spage | 7225 | en_HK |
dc.identifier.epage | 7237 | en_HK |
dc.identifier.isi | WOS:000268549400025 | - |
dc.publisher.place | Germany | en_HK |
dc.identifier.scopusauthorid | Tong, GSM=7102328656 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0947-6539 | - |