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

Journal Article · · ACS Omega
 [1];  [2];  [2];  [3];  [1]
  1. Arctic Univ. of Norway, Tromsø (Norway). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Graz Univ. of Technology, Graz (Austria). Inst. of Analytical Chemistry and Food Chemistry
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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. Finally, the quantum yield of ~0.3% is comparable to those observed for six-coordinate Ir(III) corroles.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); Research Council of Norway
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1493261
Journal Information:
ACS Omega, Journal Name: ACS Omega Journal Issue: 8 Vol. 3; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment journal October 2019
Ambient-temperature near-IR phosphorescence and potential applications of rhenium-oxo corroles journal January 2019

Figures / Tables (13)

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