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Publication . Article . 2018

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;
Open Access
English
Published: 01 Aug 2018
Publisher: American Chemical Society
Abstract

With permission from Alemayehu, A.B., McCormick, L.J.M., Gagnon, K.J., Borisov, S.M. & Ghosh, A. (2018). Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence. ACS Omega, 3(8), 9360-9368. Copyright 2018 American Chemical Society. Source at https://doi.org/10.1021/acsomega.8b01149. 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.

Subjects by Vocabulary

Microsoft Academic Graph classification: Chemistry Tris chemistry.chemical_compound Corrole Phosphorescence Platinum chemistry.chemical_element Molecule Reference electrode Quantum yield Crystallography Ground state

Subjects

VDP::Mathematics and natural science: 400::Chemistry: 440, VDP::Matematikk og Naturvitenskap: 400::Kjemi: 440, Chemical Engineering, Materials Engineering, General Chemical Engineering, General Chemistry, Article

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European Plate Observing System
  • Funder: European Commission (EC)
  • Project Code: 262229
  • Funding stream: FP7 | SP4 | INFRA
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