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

Authors: Abraham B. Alemayehu; Laura J. McCormick; Kevin J. Gagnon; Sergey M. Borisov; Abhik Ghosh;

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

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.

Countries
Norway, United States
Subjects by Vocabulary

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

Keywords

General Chemical Engineering, Article, Inorganic Chemistry, Chemical engineering, Macromolecular and materials chemistry, VDP::Mathematics and natural science: 400::Chemistry: 440, Materials Engineering, General Chemistry, Physical chemistry, VDP::Matematikk og Naturvitenskap: 400::Kjemi: 440, Chemical Sciences

78 references, page 1 of 8

(1) Ghosh, A. Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations. Chem. Rev. 2017, 117, 3798−3881.

(2) Palmer, J. H.; Durrell, A. C.; Gross, Z.; Winkler, J. R.; Gray, H. B.

Near-IR Phosphorescence of Iridium(III) Corroles at Ambient Temperature. J. Am. Chem. Soc. 2010, 132, 9230−9231.

(3) Sinha, W.; Ravotto, L.; Ceroni, P.; Kar, S. NIR-Emissive Iridium(III) Corrole Complexes as Efficient Singlet Oxygen Sensitizers. Dalton Trans. 2015, 44, 17767−17773.

(4) Borisov, S. M.; Alemayehu, A.; Ghosh, A. Osmium-Nitrido Corroles as NIR Indicators for Oxygen Sensors and Triplet Sensitizers for Organic Upconversion and Singlet Oxygen Generation. J. Mater.

Chem. C 2016, 4, 5822−5828.

(5) Lemon, C. M.; Powers, D. C.; Brothers, P. J.; Nocera, D. G. Gold Corroles as Near-IR Phosphors for Oxygen Sensing. Inorg. Chem.

(6) Alemayehu, A. B.; Day, N. U.; Mani, T.; Rudine, A. B.; Thomas, K. E.; Gederaas, O. A.; Vinogradov, S. A.; Wamser, C. C.; Ghosh, A.

Mater. Interfaces 2016, 8, 18935−18942.

(7) Teo, R. D.; Hwang, J. Y.; Termini, J.; Gross, Z.; Gray, H. B.

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    Top 10%
    influence
    This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
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    This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
    Top 10%
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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
27
Top 10%
Average
Top 10%
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EC| EPOS
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EPOS
European Plate Observing System
  • Funder: European Commission (EC)
  • Project Code: 262229
  • Funding stream: FP7 | SP4 | INFRA
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