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Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex.

Publication ,  Journal Article
Redmore, NP; Rubtsov, IV; Therien, MJ
Published in: Inorganic chemistry
February 2002

N-[5-(10,20-Diphenylporphinato)zinc(II)]-N'-(octyl)pyromellitic diimide (PZn-PI), a meso-pyromellitimide-substituted (porphinato)zinc(II) compound, has been fabricated from the reaction of (5-amino-10,20-diphenylporphinato)zinc(II) with pyromellitic dianhydride in the presence of octylamine. Interrogation of the photoinduced charge separation (CS) and thermal charge recombination (CR) electron-transfer (ET) dynamics for PZn-PI in CH(2)Cl(2) via pump-probe transient absorption spectroscopic methods shows that tau(CS) and tau(CR) are 770 and 5200 fs, respectively. These ET dynamics differ from those elucidated previously for closely related 5-quinonyl-substituted (porphinato)metal compounds, and derive from the fact that the low-lying excited states for PZn-PI are porphyrin-localized, possessing little charge-transfer character. The synthesis of N-(5-[15-(2-(triisopropylsilyl)ethynyl)-10,20-diphenylporphinato]zinc(II))-N'-(octyl)pyromellitic diimide demonstrates that PZn-PI can be halogenated at its 15-meso-position and used subsequently as a substrate in metal-catalyzed cross-coupling reactions; the reactivity of PZn-PI is unusual with respect to many directly linked donor-acceptor compounds in that it is stable to these oxidizing and reducing reaction conditions.

Duke Scholars

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

February 2002

Volume

41

Issue

3

Start / End Page

566 / 570

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry
 

Citation

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Redmore, N. P., Rubtsov, I. V., & Therien, M. J. (2002). Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex. Inorganic Chemistry, 41(3), 566–570. https://doi.org/10.1021/ic0108641
Redmore, Naomi P., Igor V. Rubtsov, and Michael J. Therien. “Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex.Inorganic Chemistry 41, no. 3 (February 2002): 566–70. https://doi.org/10.1021/ic0108641.
Redmore NP, Rubtsov IV, Therien MJ. Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex. Inorganic chemistry. 2002 Feb;41(3):566–70.
Redmore, Naomi P., et al. “Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex.Inorganic Chemistry, vol. 41, no. 3, Feb. 2002, pp. 566–70. Epmc, doi:10.1021/ic0108641.
Redmore NP, Rubtsov IV, Therien MJ. Synthesis, excited-state dynamics, and reactivity of a directly-linked pyromellitimide-(porphinato)zinc(II) complex. Inorganic chemistry. 2002 Feb;41(3):566–570.
Journal cover image

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

February 2002

Volume

41

Issue

3

Start / End Page

566 / 570

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry