Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex: Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion

Syed S. Razi, Yun Hee Koo, Woojae Kim, Wenbo Yang, Zhijia Wang, Habtom Gobeze, Francis D'Souza, Jianzhang Zhao, Dongho Kim

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, Förster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.

Original languageEnglish
Pages (from-to)4877-4890
Number of pages14
JournalInorganic Chemistry
Volume57
Issue number9
DOIs
Publication statusPublished - 2018 May 7

Fingerprint

Boron
Schiff Bases
Energy transfer
imines
boron
energy transfer
shift
synthesis
Photosensitizing Agents
excitation
atomic energy levels
dipyrromethane
life (durability)
Excitation energy
Quantum yield
Absorption spectroscopy
Band structure
energy bands
absorption spectroscopy
Spectroscopy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Razi, Syed S. ; Koo, Yun Hee ; Kim, Woojae ; Yang, Wenbo ; Wang, Zhijia ; Gobeze, Habtom ; D'Souza, Francis ; Zhao, Jianzhang ; Kim, Dongho. / Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex : Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 9. pp. 4877-4890.
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abstract = "A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, F{\"o}rster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10{\%} was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.",
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Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex : Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion. / Razi, Syed S.; Koo, Yun Hee; Kim, Woojae; Yang, Wenbo; Wang, Zhijia; Gobeze, Habtom; D'Souza, Francis; Zhao, Jianzhang; Kim, Dongho.

In: Inorganic Chemistry, Vol. 57, No. 9, 07.05.2018, p. 4877-4890.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ping-Pong Energy Transfer in a Boron Dipyrromethane Containing Pt(II)-Schiff Base Complex

T2 - Synthesis, Photophysical Studies, and Anti-Stokes Shift Increase in Triplet-Triplet Annihilation Upconversion

AU - Razi, Syed S.

AU - Koo, Yun Hee

AU - Kim, Woojae

AU - Yang, Wenbo

AU - Wang, Zhijia

AU - Gobeze, Habtom

AU - D'Souza, Francis

AU - Zhao, Jianzhang

AU - Kim, Dongho

PY - 2018/5/7

Y1 - 2018/5/7

N2 - A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, Förster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.

AB - A boron dipyrromethane (BDP)-containing Pt(II)-Schiff base complex (Pt-BDP), showing ping-pong singlet-triplet energy transfer, was synthesized, and the detailed photophysical properties were investigated using various steady-state and time-resolved transient spectroscopies. Femtosecond/nanosecond transient absorption spectroscopies demonstrated that, upon selective excitation of the BDP unit in Pt-BDP at 490 nm, Förster resonance energy transfer from the BDP unit to the Pt(II) coordination center occurred (6.7 ps), accompanied by an ultrafast intersystem crossing at the Pt(II) coordination center (<1 ps) and triplet-triplet energy transfer back to the BDP moiety (148 ps). These processes generated a triplet state localized at BDP, and the lifetime was 103.2 μs, much longer than the triplet-state lifetime of Pt-Ph (3.5 μs), a complex without the BDP moiety. Finally, Pt-BDP was used as a triplet photosensitizer for triplet-triplet annihilation (TTA) upconversion through selective excitation of the BDP unit or the Pt(II) coordination center at lower excitation energy. An upconversion quantum yield of up to 10% was observed with selective excitation of the BDP moiety, and a large anti-Stokes shift of 0.65 eV was observed upon excitation of the lower-energy band of the Pt(II) coordination center. We propose that using triplet photosensitizers with the ping-pong energy-transfer process may become a useful method for increasing the anti-Stokes shift of TTA upconversion.

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