Broadband Visible Light Harvesting N^N Pt(II) Bisacetylide Complex with Bodipy and Naphthalene Diimide Ligands: Förster Resonance Energy Transfer and Intersystem Crossing

Peili Wang, Yun Hee Koo, Woojae Kim, Wenbo Yang, Xiaoneng Cui, Wei Ji, Jianzhang Zhao, Dongho Kim

Research output: Contribution to journalArticle

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Abstract

A N^N Pt(II) complex, Pt-1, with two heteroleptic ligands was prepared, which is a rarely reported molecular structure. The two different acetylide ligands, i.e., boron-dipyyromethane (BDP) and naphthalenediimide (NDI) chromophores, show strong absorption in the visible region. The photophysical properties of the complex were investigated by using steady-state and femtosecond/nanosecond time-resolved optical spectroscopies, as well as electrochemical characterization. Upon selective photoexcitation of the coordinated BDP acetylide ligand at 503 nm, the Förster-resonance energy transfer (FRET, k FRET = 1.2 × 10 11 s -1 ) process from the BDP to NDI ligand was observed, which leads to the population of the singlet excited state of the latter. After that, intersystem crossing (ISC) process occurs (k ISC = 3.3 × 10 9 s -1 ), which generates the triplet excited state of the NDI ligand (τ = 28.1 μs). The overall excited-state dynamics are fairly similar in both nonpolar toluene and polar benzonitrile, indicating that photoinduced charge separation dynamics between BDP and NDI is insignificant. This is presumably due to the strong interaction between the NDI ligand and central Pt atom which can give rise to strong spin-orbit coupling. This hypothesis can be further supported by the excited-state dynamics obtained after photoexcitation at the S 2 state of the NDI ligand. The ultrafast ISC from the S 2 state of the NDI ligand to a higher triplet state, which corresponds to the breakdown of the Kasha-Vavilov's rule, was observed, suggesting that the NDI core strongly interacts with the heavy Pt atom. Finally, we identified that this broadband visible light-excitable Pt(II) complex can be used as a triplet photosensitizer for two-color excitable triplet-triplet annihilation upconversion, and the upconversion quantum yield was determined as 4.1%.

Original languageEnglish
Pages (from-to)11117-11128
Number of pages12
JournalJournal of Physical Chemistry C
Volume121
Issue number21
DOIs
Publication statusPublished - 2017 Jun 1

Fingerprint

Naphthalene
naphthalene
Energy transfer
energy transfer
Ligands
broadband
ligands
Boron
Excited states
boron
Photoexcitation
photoexcitation
excitation
Atoms
Photosensitizing Agents
Photosensitizers
naphthalenediimide
Toluene
Quantum yield
polarization (charge separation)

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Wang, Peili ; Koo, Yun Hee ; Kim, Woojae ; Yang, Wenbo ; Cui, Xiaoneng ; Ji, Wei ; Zhao, Jianzhang ; Kim, Dongho. / Broadband Visible Light Harvesting N^N Pt(II) Bisacetylide Complex with Bodipy and Naphthalene Diimide Ligands : Förster Resonance Energy Transfer and Intersystem Crossing. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 21. pp. 11117-11128.
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abstract = "A N^N Pt(II) complex, Pt-1, with two heteroleptic ligands was prepared, which is a rarely reported molecular structure. The two different acetylide ligands, i.e., boron-dipyyromethane (BDP) and naphthalenediimide (NDI) chromophores, show strong absorption in the visible region. The photophysical properties of the complex were investigated by using steady-state and femtosecond/nanosecond time-resolved optical spectroscopies, as well as electrochemical characterization. Upon selective photoexcitation of the coordinated BDP acetylide ligand at 503 nm, the F{\"o}rster-resonance energy transfer (FRET, k FRET = 1.2 × 10 11 s -1 ) process from the BDP to NDI ligand was observed, which leads to the population of the singlet excited state of the latter. After that, intersystem crossing (ISC) process occurs (k ISC = 3.3 × 10 9 s -1 ), which generates the triplet excited state of the NDI ligand (τ = 28.1 μs). The overall excited-state dynamics are fairly similar in both nonpolar toluene and polar benzonitrile, indicating that photoinduced charge separation dynamics between BDP and NDI is insignificant. This is presumably due to the strong interaction between the NDI ligand and central Pt atom which can give rise to strong spin-orbit coupling. This hypothesis can be further supported by the excited-state dynamics obtained after photoexcitation at the S 2 state of the NDI ligand. The ultrafast ISC from the S 2 state of the NDI ligand to a higher triplet state, which corresponds to the breakdown of the Kasha-Vavilov's rule, was observed, suggesting that the NDI core strongly interacts with the heavy Pt atom. Finally, we identified that this broadband visible light-excitable Pt(II) complex can be used as a triplet photosensitizer for two-color excitable triplet-triplet annihilation upconversion, and the upconversion quantum yield was determined as 4.1{\%}.",
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Broadband Visible Light Harvesting N^N Pt(II) Bisacetylide Complex with Bodipy and Naphthalene Diimide Ligands : Förster Resonance Energy Transfer and Intersystem Crossing. / Wang, Peili; Koo, Yun Hee; Kim, Woojae; Yang, Wenbo; Cui, Xiaoneng; Ji, Wei; Zhao, Jianzhang; Kim, Dongho.

In: Journal of Physical Chemistry C, Vol. 121, No. 21, 01.06.2017, p. 11117-11128.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Broadband Visible Light Harvesting N^N Pt(II) Bisacetylide Complex with Bodipy and Naphthalene Diimide Ligands

T2 - Förster Resonance Energy Transfer and Intersystem Crossing

AU - Wang, Peili

AU - Koo, Yun Hee

AU - Kim, Woojae

AU - Yang, Wenbo

AU - Cui, Xiaoneng

AU - Ji, Wei

AU - Zhao, Jianzhang

AU - Kim, Dongho

PY - 2017/6/1

Y1 - 2017/6/1

N2 - A N^N Pt(II) complex, Pt-1, with two heteroleptic ligands was prepared, which is a rarely reported molecular structure. The two different acetylide ligands, i.e., boron-dipyyromethane (BDP) and naphthalenediimide (NDI) chromophores, show strong absorption in the visible region. The photophysical properties of the complex were investigated by using steady-state and femtosecond/nanosecond time-resolved optical spectroscopies, as well as electrochemical characterization. Upon selective photoexcitation of the coordinated BDP acetylide ligand at 503 nm, the Förster-resonance energy transfer (FRET, k FRET = 1.2 × 10 11 s -1 ) process from the BDP to NDI ligand was observed, which leads to the population of the singlet excited state of the latter. After that, intersystem crossing (ISC) process occurs (k ISC = 3.3 × 10 9 s -1 ), which generates the triplet excited state of the NDI ligand (τ = 28.1 μs). The overall excited-state dynamics are fairly similar in both nonpolar toluene and polar benzonitrile, indicating that photoinduced charge separation dynamics between BDP and NDI is insignificant. This is presumably due to the strong interaction between the NDI ligand and central Pt atom which can give rise to strong spin-orbit coupling. This hypothesis can be further supported by the excited-state dynamics obtained after photoexcitation at the S 2 state of the NDI ligand. The ultrafast ISC from the S 2 state of the NDI ligand to a higher triplet state, which corresponds to the breakdown of the Kasha-Vavilov's rule, was observed, suggesting that the NDI core strongly interacts with the heavy Pt atom. Finally, we identified that this broadband visible light-excitable Pt(II) complex can be used as a triplet photosensitizer for two-color excitable triplet-triplet annihilation upconversion, and the upconversion quantum yield was determined as 4.1%.

AB - A N^N Pt(II) complex, Pt-1, with two heteroleptic ligands was prepared, which is a rarely reported molecular structure. The two different acetylide ligands, i.e., boron-dipyyromethane (BDP) and naphthalenediimide (NDI) chromophores, show strong absorption in the visible region. The photophysical properties of the complex were investigated by using steady-state and femtosecond/nanosecond time-resolved optical spectroscopies, as well as electrochemical characterization. Upon selective photoexcitation of the coordinated BDP acetylide ligand at 503 nm, the Förster-resonance energy transfer (FRET, k FRET = 1.2 × 10 11 s -1 ) process from the BDP to NDI ligand was observed, which leads to the population of the singlet excited state of the latter. After that, intersystem crossing (ISC) process occurs (k ISC = 3.3 × 10 9 s -1 ), which generates the triplet excited state of the NDI ligand (τ = 28.1 μs). The overall excited-state dynamics are fairly similar in both nonpolar toluene and polar benzonitrile, indicating that photoinduced charge separation dynamics between BDP and NDI is insignificant. This is presumably due to the strong interaction between the NDI ligand and central Pt atom which can give rise to strong spin-orbit coupling. This hypothesis can be further supported by the excited-state dynamics obtained after photoexcitation at the S 2 state of the NDI ligand. The ultrafast ISC from the S 2 state of the NDI ligand to a higher triplet state, which corresponds to the breakdown of the Kasha-Vavilov's rule, was observed, suggesting that the NDI core strongly interacts with the heavy Pt atom. Finally, we identified that this broadband visible light-excitable Pt(II) complex can be used as a triplet photosensitizer for two-color excitable triplet-triplet annihilation upconversion, and the upconversion quantum yield was determined as 4.1%.

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