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Stable platinum(IV) corroles: Synthesis, molecular structure, and room-temperature near-IR phosphorescence

Stable platinum(IV) corroles: Synthesis, molecular structure, and room-temperature near-IR phosphorescence
Stable platinum(IV) corroles: Synthesis, molecular structure, and room-temperature near-IR phosphorescence

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.

2470-1343
9360-9368
Alemayehu, Abraham B.
87f64bd7-bb09-4f76-a631-b0991665ad3e
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Gagnon, Kevin J.
5535af49-cc12-48b8-b007-28bb1f1b070c
Borisov, Sergey M.
eceeb922-0fb8-4425-813e-71cd23601921
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7
Alemayehu, Abraham B.
87f64bd7-bb09-4f76-a631-b0991665ad3e
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Gagnon, Kevin J.
5535af49-cc12-48b8-b007-28bb1f1b070c
Borisov, Sergey M.
eceeb922-0fb8-4425-813e-71cd23601921
Ghosh, Abhik
01a311da-a139-43f0-ae29-0efa0e8788f7

Alemayehu, Abraham B., McCormick, Laura J., Gagnon, Kevin J., Borisov, Sergey M. and Ghosh, Abhik (2018) Stable platinum(IV) corroles: Synthesis, molecular structure, and room-temperature near-IR phosphorescence. ACS Omega, 3 (8), 9360-9368. (doi:10.1021/acsomega.8b01149).

Record type: Article

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.

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Published date: 31 August 2018

Identifiers

Local EPrints ID: 438917
URI: http://eprints.soton.ac.uk/id/eprint/438917
ISSN: 2470-1343
PURE UUID: c6feef78-a114-4331-b801-1dd9c3bcdefb
ORCID for Laura J. McCormick: ORCID iD orcid.org/0000-0002-6634-4717

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Date deposited: 26 Mar 2020 17:35
Last modified: 26 Nov 2021 03:21

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Contributors

Author: Abraham B. Alemayehu
Author: Kevin J. Gagnon
Author: Sergey M. Borisov
Author: Abhik Ghosh

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