Effects of carbon-metal-carbon linkages on the optical, photophysical, and electrochemical properties of phosphametallacycle-linked coplanar porphyrin dimers

Yoshihiro Matano, Kazuaki Matsumoto, Hironobu Hayashi, Yoshihide Nakao, Tatu Kumpulainen, Vladimir Chukharev, Nikolai V. Tkachenko, Helge Lemmetyinen, Soji Shimizu, Nagao Kobayashi, Daisuke Sakamaki, Akihiro Ito, Kazuyoshi Tanaka, Hiroshi Imahori

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Abstract

5-(Diphenylphosphanyl)-10,15,20-triarylporphyrins (meso- phosphanylporphyrins) underwent complexations with palladium(II) and platinum(II) salts to afford phosphapalladacycle- and phosphaplatinacycle-fused coplanar porphyrin dimers, respectively, via regioselective peripheral β-C-H activation of the meso-phosphanylporphyrin ligands. The optical and electrochemical properties of these metal-linked porphyrin dimers as well as their porphyrin monomer/dimer references were investigated by means of steady-state UV-vis absorption/fluorescence spectroscopy, cyclic and differential pulse voltammetry, time-resolved spectroscopy (fluorescence and transient absorption lifetimes and spectra), and magnetic circular dichroism spectroscopy. All the observed data clearly show that the palladium(II) and platinum(II) linkers play crucial roles in the electronic communication between two porphyrin chromophores at the one-electron oxidized state and in the singlet-triplet intersystem-crossing process at the excited state. It has also been revealed that the C-Pt-C linkage makes more significant impacts on these fundamental properties than the C-Pd-C linkage. Furthermore, density functional theory calculations on the metal-linked porphyrin dimers have suggested that the antibonding dπ-pπ orbital interaction between the peripherally attached metal and adjacent pyrrolic β-carbon atoms destabilizes the highest occupied molecular orbitals of the porphyrin π-systems and accounts for the observed unique absorption properties. On the basis of these experimental and theoretical results, it can be concluded that the linear carbon-metal-carbon linkages weakly but definitely perturb the optical, photophysical, and electrochemical properties of the phosphametallacycle-linked coplanar porphyrin dimers.

Original languageEnglish
Pages (from-to)1825-1839
Number of pages15
JournalJournal of the American Chemical Society
Volume134
Issue number3
DOIs
Publication statusPublished - Jan 25 2012

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Porphyrins
Electrochemical properties
Dimers
Carbon
Optical properties
Metals
Fluorescence Spectrometry
Fluorescence spectroscopy
Palladium
Platinum
Circular dichroism spectroscopy
Molecular orbitals
Voltammetry
Chromophores
Circular Dichroism
Complexation
Absorption spectroscopy
Excited states
Electron energy levels
Density functional theory

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Effects of carbon-metal-carbon linkages on the optical, photophysical, and electrochemical properties of phosphametallacycle-linked coplanar porphyrin dimers. / Matano, Yoshihiro; Matsumoto, Kazuaki; Hayashi, Hironobu; Nakao, Yoshihide; Kumpulainen, Tatu; Chukharev, Vladimir; Tkachenko, Nikolai V.; Lemmetyinen, Helge; Shimizu, Soji; Kobayashi, Nagao; Sakamaki, Daisuke; Ito, Akihiro; Tanaka, Kazuyoshi; Imahori, Hiroshi.

In: Journal of the American Chemical Society, Vol. 134, No. 3, 25.01.2012, p. 1825-1839.

Research output: Contribution to journalArticle

Matano, Y, Matsumoto, K, Hayashi, H, Nakao, Y, Kumpulainen, T, Chukharev, V, Tkachenko, NV, Lemmetyinen, H, Shimizu, S, Kobayashi, N, Sakamaki, D, Ito, A, Tanaka, K & Imahori, H 2012, 'Effects of carbon-metal-carbon linkages on the optical, photophysical, and electrochemical properties of phosphametallacycle-linked coplanar porphyrin dimers', Journal of the American Chemical Society, vol. 134, no. 3, pp. 1825-1839. https://doi.org/10.1021/ja210205v
Matano, Yoshihiro ; Matsumoto, Kazuaki ; Hayashi, Hironobu ; Nakao, Yoshihide ; Kumpulainen, Tatu ; Chukharev, Vladimir ; Tkachenko, Nikolai V. ; Lemmetyinen, Helge ; Shimizu, Soji ; Kobayashi, Nagao ; Sakamaki, Daisuke ; Ito, Akihiro ; Tanaka, Kazuyoshi ; Imahori, Hiroshi. / Effects of carbon-metal-carbon linkages on the optical, photophysical, and electrochemical properties of phosphametallacycle-linked coplanar porphyrin dimers. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 3. pp. 1825-1839.
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T1 - Effects of carbon-metal-carbon linkages on the optical, photophysical, and electrochemical properties of phosphametallacycle-linked coplanar porphyrin dimers

AU - Matano, Yoshihiro

AU - Matsumoto, Kazuaki

AU - Hayashi, Hironobu

AU - Nakao, Yoshihide

AU - Kumpulainen, Tatu

AU - Chukharev, Vladimir

AU - Tkachenko, Nikolai V.

AU - Lemmetyinen, Helge

AU - Shimizu, Soji

AU - Kobayashi, Nagao

AU - Sakamaki, Daisuke

AU - Ito, Akihiro

AU - Tanaka, Kazuyoshi

AU - Imahori, Hiroshi

PY - 2012/1/25

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