Electronic infrared light absorption of a tri-palladium complex containing two π-expanded tetracene ligands

Tsuyoshi Suzuki; Takafumi Nakagawa; Kei Ohkubo; Shunichi Fukuzumi; Yutaka Matsuo

doi:10.1039/c4sc02018a

Electronic infrared light absorption of a tri-palladium complex containing two π-expanded tetracene ligands

Tsuyoshi Suzuki, Takafumi Nakagawa, Kei Ohkubo, Shunichi Fukuzumi, Yutaka Matsuo

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

A large π-electron conjugated system consisting of three bridging palladium metals and two π-expanded tetracene derivatives was synthesized to have a narrow HOMO-LUMO gap for long-wavelength light absorption. The product, Pd₃(TIDS)₂(PPh₃)₄ (TIDS = tetracene imide disulfide), showed far long-wavelength light absorption reaching the infrared region (absorption maximum = 1982 nm, ε = 4.0 × 10⁴ M^-1 cm^-1 in CH₂Cl₂ solution; 2500 nm in the solid state). X-ray crystallography revealed a tri-metallic structure composed of three square-planar Pd coordination planes. The total oxidation number of the three Pd atoms is +4. Quantum chemical calculations were used to elucidate wholly delocalized π-conjugation in the non-coplanar structure and the HOMO-LUMO transition for this unique absorption band. Time-resolved transient absorption measurements revealed the excited state dynamics characterized by a triplet charge transfer state lifetime of 400 ps and a λ_max of 1280 nm. A mononuclear Pd complex, Pd(TIDS)(PPh₃)₂, was also synthesized as a reference compound, and characterized with spectroscopic and X-ray crystallographic analyses.

Original language	English
Pages (from-to)	4888-4894
Number of pages	7
Journal	Chemical Science
Volume	5
Issue number	12
DOIs	https://doi.org/10.1039/c4sc02018a
State	Published - 1 Dec 2014

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title = "Electronic infrared light absorption of a tri-palladium complex containing two π-expanded tetracene ligands",

abstract = "A large π-electron conjugated system consisting of three bridging palladium metals and two π-expanded tetracene derivatives was synthesized to have a narrow HOMO-LUMO gap for long-wavelength light absorption. The product, Pd3(TIDS)2(PPh3)4 (TIDS = tetracene imide disulfide), showed far long-wavelength light absorption reaching the infrared region (absorption maximum = 1982 nm, ε = 4.0 × 104 M-1 cm-1 in CH2Cl2 solution; 2500 nm in the solid state). X-ray crystallography revealed a tri-metallic structure composed of three square-planar Pd coordination planes. The total oxidation number of the three Pd atoms is +4. Quantum chemical calculations were used to elucidate wholly delocalized π-conjugation in the non-coplanar structure and the HOMO-LUMO transition for this unique absorption band. Time-resolved transient absorption measurements revealed the excited state dynamics characterized by a triplet charge transfer state lifetime of 400 ps and a λmax of 1280 nm. A mononuclear Pd complex, Pd(TIDS)(PPh3)2, was also synthesized as a reference compound, and characterized with spectroscopic and X-ray crystallographic analyses.",

author = "Tsuyoshi Suzuki and Takafumi Nakagawa and Kei Ohkubo and Shunichi Fukuzumi and Yutaka Matsuo",

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AU - Suzuki, Tsuyoshi

AU - Nakagawa, Takafumi

AU - Ohkubo, Kei

AU - Fukuzumi, Shunichi

AU - Matsuo, Yutaka

PY - 2014/12/1

Y1 - 2014/12/1

N2 - A large π-electron conjugated system consisting of three bridging palladium metals and two π-expanded tetracene derivatives was synthesized to have a narrow HOMO-LUMO gap for long-wavelength light absorption. The product, Pd3(TIDS)2(PPh3)4 (TIDS = tetracene imide disulfide), showed far long-wavelength light absorption reaching the infrared region (absorption maximum = 1982 nm, ε = 4.0 × 104 M-1 cm-1 in CH2Cl2 solution; 2500 nm in the solid state). X-ray crystallography revealed a tri-metallic structure composed of three square-planar Pd coordination planes. The total oxidation number of the three Pd atoms is +4. Quantum chemical calculations were used to elucidate wholly delocalized π-conjugation in the non-coplanar structure and the HOMO-LUMO transition for this unique absorption band. Time-resolved transient absorption measurements revealed the excited state dynamics characterized by a triplet charge transfer state lifetime of 400 ps and a λmax of 1280 nm. A mononuclear Pd complex, Pd(TIDS)(PPh3)2, was also synthesized as a reference compound, and characterized with spectroscopic and X-ray crystallographic analyses.

AB - A large π-electron conjugated system consisting of three bridging palladium metals and two π-expanded tetracene derivatives was synthesized to have a narrow HOMO-LUMO gap for long-wavelength light absorption. The product, Pd3(TIDS)2(PPh3)4 (TIDS = tetracene imide disulfide), showed far long-wavelength light absorption reaching the infrared region (absorption maximum = 1982 nm, ε = 4.0 × 104 M-1 cm-1 in CH2Cl2 solution; 2500 nm in the solid state). X-ray crystallography revealed a tri-metallic structure composed of three square-planar Pd coordination planes. The total oxidation number of the three Pd atoms is +4. Quantum chemical calculations were used to elucidate wholly delocalized π-conjugation in the non-coplanar structure and the HOMO-LUMO transition for this unique absorption band. Time-resolved transient absorption measurements revealed the excited state dynamics characterized by a triplet charge transfer state lifetime of 400 ps and a λmax of 1280 nm. A mononuclear Pd complex, Pd(TIDS)(PPh3)2, was also synthesized as a reference compound, and characterized with spectroscopic and X-ray crystallographic analyses.

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JO - Chemical Science

JF - Chemical Science

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ER -

Electronic infrared light absorption of a tri-palladium complex containing two π-expanded tetracene ligands

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