Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence

Abraham B. Alemayehu, Laura J. McCormick, Kevin J. Gagnon, Sergey M. Borisov, Abhik Ghosh

Research output: Contribution to journalArticleResearchpeer-review

Abstract

A series of stable Pt(IV) corrole complexes with the general formula PtIV[TpXPC](m/p-C6H4CN)(py), where TpXPC3- is the trianion of a tris(p-X-phenyl)corrole and X = CF3, H, and CH3, has been synthesized, affording key physicochemical data on a rare and elusive class of metallocorroles. Single-crystal X-ray structures of two of the complexes revealed very short equatorial Pt-N distances of 1.94-1.97 Å, an axial Pt-C distance of ∼2.03 Å, and an axial Pt-N distance of ∼2.22 Å. The complexes exhibit Soret maxima at ∼430 nm, which are essentially independent of the meso-aryl para substituents, and strong Q bands with the most intense peak at 595-599 nm. The substituent-independent Soret maxima are consistent with an innocent PtIV-corrole3- description for the complexes. The low reduction potentials (-1.45 ± 0.08 V vs saturated calomel reference electrode) also support a highly stable Pt(IV) ground state as opposed to a noninnocent corrole•2- description. The reductions, however, are irreversible, which suggests that they involve concomitant cleavage of the Pt-aryl bond. Unlike Pt(IV) porphyrins, two of the complexes, PtIV[TpXPC](m-C6H4CN)(py) (X = CF3 and CH3), were found to exhibit room-temperature near-IR phosphorescence with emission maxima at 813 and 826 nm, respectively. The quantum yield of ∼0.3% is comparable to those observed for six-coordinate Ir(III) corroles.

Original languageEnglish
Pages (from-to)9360-9368
Number of pages9
JournalACS Omega
Volume3
Issue number8
DOIs
Publication statusPublished - 31 Aug 2018

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Phosphorescence
Platinum
Molecular structure
Porphyrins
Quantum yield
Ground state
Single crystals
X rays
Temperature
Electrodes
corrole

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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Stable Platinum(IV) Corroles : Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence. / Alemayehu, Abraham B.; McCormick, Laura J.; Gagnon, Kevin J.; Borisov, Sergey M.; Ghosh, Abhik.

In: ACS Omega, Vol. 3, No. 8, 31.08.2018, p. 9360-9368.

Research output: Contribution to journalArticleResearchpeer-review

Alemayehu, Abraham B. ; McCormick, Laura J. ; Gagnon, Kevin J. ; Borisov, Sergey M. ; Ghosh, Abhik. / Stable Platinum(IV) Corroles : Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence. In: ACS Omega. 2018 ; Vol. 3, No. 8. pp. 9360-9368.
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abstract = "A series of stable Pt(IV) corrole complexes with the general formula PtIV[TpXPC](m/p-C6H4CN)(py), where TpXPC3- is the trianion of a tris(p-X-phenyl)corrole and X = CF3, H, and CH3, has been synthesized, affording key physicochemical data on a rare and elusive class of metallocorroles. Single-crystal X-ray structures of two of the complexes revealed very short equatorial Pt-N distances of 1.94-1.97 {\AA}, an axial Pt-C distance of ∼2.03 {\AA}, and an axial Pt-N distance of ∼2.22 {\AA}. The complexes exhibit Soret maxima at ∼430 nm, which are essentially independent of the meso-aryl para substituents, and strong Q bands with the most intense peak at 595-599 nm. The substituent-independent Soret maxima are consistent with an innocent PtIV-corrole3- description for the complexes. The low reduction potentials (-1.45 ± 0.08 V vs saturated calomel reference electrode) also support a highly stable Pt(IV) ground state as opposed to a noninnocent corrole•2- description. The reductions, however, are irreversible, which suggests that they involve concomitant cleavage of the Pt-aryl bond. Unlike Pt(IV) porphyrins, two of the complexes, PtIV[TpXPC](m-C6H4CN)(py) (X = CF3 and CH3), were found to exhibit room-temperature near-IR phosphorescence with emission maxima at 813 and 826 nm, respectively. The quantum yield of ∼0.3{\%} is comparable to those observed for six-coordinate Ir(III) corroles.",
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