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


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.

SUBMITTER: Alemayehu AB 

PROVIDER: S-EPMC6645213 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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

Alemayehu Abraham B AB   McCormick Laura J LJ   Gagnon Kevin J KJ   Borisov Sergey M SM   Ghosh Abhik A  

ACS omega 20180817 8


A series of stable Pt(IV) corrole complexes with the general formula Pt<sup>IV</sup>[T<i>p</i>XPC](<i>m</i>/<i>p</i>-C<sub>6</sub>H<sub>4</sub>CN)(py), where T<i>p</i>XPC<sup>3-</sup> is the trianion of a tris(<i>p</i>-X-phenyl)corrole and X = CF<sub>3</sub>, H, and CH<sub>3</sub>, 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.  ...[more]

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