Anthryl-Appended Platinum(II) Schiff Base Complexes : Exceptionally Small Stokes Shift, Triplet Excited States Equilibrium, and Application in Triplet-Triplet-Annihilation Upconversion
Two anthryl platinum(II) N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-benzenediamine Schiff base complexes were synthesized, with the anthryl attached via its 9 position (Pt-9An) or 2 position (Pt-2An) to the platinum (Pt) Schiff base backbone. The complexes show unusually small Stokes shifts (0.23 eV), representing a very small energy loss for the photoexcitation/intersystem crossing process, which is beneficial for applications as triplet photosensitizers. Phosphorescence of the Pt(II) coordination framework (ΦP = 11.0%) is quenched in the anthryl-containing complexes (ΦP = 4.0%) and shows a biexponential decay (τP = 3.4 μs/87% and 18.2 μs/13%) compared to the single-exponential decay of the native Pt(II) Schiff base complex (τP = 3.7 μs). Femtosecond/nanosecond transient absorption spectroscopy suggests an equilibrium between triplet anthracene (3An) and triplet metal-to-ligand charge-transfer (3MLCT) states, with the dark 3An state slightly lower in energy (1.96 eV for Pt-9An and 1.90 eV for Pt-2An) than the emissive 3MLCT state (1.97 eV for Pt-9An and 1.91 eV for Pt-2An). Intramolecular triplet-triplet energy transfer (TTET) and reverse TTET take 4.8 ps/444 ps for Pt-9An and 55 ps/1.7 ns for Pt-2An, respectively. The triplet-state equilibrium extends the triplet-state lifetime of the complexes to 103 μs (Pt-2An) or 163 μs (Pt-9An), in comparison to the native Pt(II) complex, which shows a lifetime of 4.0 μs. The complexes were used for triplet-triplet-annihilation upconversion with perylene as the triplet acceptor. The upconversion quantum yield is up to 15%, and a large anti-Stokes shift (0.75 eV) is achieved by excitation into the singlet metal-to-ligand charge-transfer absorption band (589 nm) of the complexes (anti-Stokes shift is 0.92 eV with 9,10-diphenylanthracene as the acceptor).
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
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| Enthalten in: |
Inorganic chemistry - 59(2020), 20 vom: 19. Okt., Seite 14731-14745 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Chen, Kepeng [VerfasserIn] |
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| Anmerkungen: |
Date Revised 19.10.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.0c01932 |
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| Förderinstitution / Projekttitel: |
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NLM31438099X |
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| 100 | 1 | |a Chen, Kepeng |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Anthryl-Appended Platinum(II) Schiff Base Complexes |b Exceptionally Small Stokes Shift, Triplet Excited States Equilibrium, and Application in Triplet-Triplet-Annihilation Upconversion |
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| 500 | |a Date Revised 19.10.2020 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Two anthryl platinum(II) N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-benzenediamine Schiff base complexes were synthesized, with the anthryl attached via its 9 position (Pt-9An) or 2 position (Pt-2An) to the platinum (Pt) Schiff base backbone. The complexes show unusually small Stokes shifts (0.23 eV), representing a very small energy loss for the photoexcitation/intersystem crossing process, which is beneficial for applications as triplet photosensitizers. Phosphorescence of the Pt(II) coordination framework (ΦP = 11.0%) is quenched in the anthryl-containing complexes (ΦP = 4.0%) and shows a biexponential decay (τP = 3.4 μs/87% and 18.2 μs/13%) compared to the single-exponential decay of the native Pt(II) Schiff base complex (τP = 3.7 μs). Femtosecond/nanosecond transient absorption spectroscopy suggests an equilibrium between triplet anthracene (3An) and triplet metal-to-ligand charge-transfer (3MLCT) states, with the dark 3An state slightly lower in energy (1.96 eV for Pt-9An and 1.90 eV for Pt-2An) than the emissive 3MLCT state (1.97 eV for Pt-9An and 1.91 eV for Pt-2An). Intramolecular triplet-triplet energy transfer (TTET) and reverse TTET take 4.8 ps/444 ps for Pt-9An and 55 ps/1.7 ns for Pt-2An, respectively. The triplet-state equilibrium extends the triplet-state lifetime of the complexes to 103 μs (Pt-2An) or 163 μs (Pt-9An), in comparison to the native Pt(II) complex, which shows a lifetime of 4.0 μs. The complexes were used for triplet-triplet-annihilation upconversion with perylene as the triplet acceptor. The upconversion quantum yield is up to 15%, and a large anti-Stokes shift (0.75 eV) is achieved by excitation into the singlet metal-to-ligand charge-transfer absorption band (589 nm) of the complexes (anti-Stokes shift is 0.92 eV with 9,10-diphenylanthracene as the acceptor) | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Hussain, Mushraf |e verfasserin |4 aut | |
| 700 | 1 | |a Razi, Syed S |e verfasserin |4 aut | |
| 700 | 1 | |a Hou, Yuqi |e verfasserin |4 aut | |
| 700 | 1 | |a Yildiz, Elif Akhuseyin |e verfasserin |4 aut | |
| 700 | 1 | |a Zhao, Jianzhang |e verfasserin |4 aut | |
| 700 | 1 | |a Yaglioglu, Halime Gul |e verfasserin |4 aut | |
| 700 | 1 | |a Donato, Mariangela Di |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:59 |g year:2020 |g number:20 |g day:19 |g month:10 |g pages:14731-14745 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.0c01932 |3 Volltext |
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