Photophysical Properties of Near-Infrared Phosphorescent π-Extended Platinum Porphyrins

Sommer, Jonathan R.; Shelton, Abigail H.; Parthasarathy, Anand; Ghiviriga, Ion; Reynolds, John R.; Schanze, Kirk S.

doi:10.1021/cm202241e

Cited by 150 publications

(121 citation statements)

References 37 publications

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“…All TATBPs synthesized in this work show the typical absorption and emission features (see Supporting Information), which have already been described in literature . However, the majority of publications describes the characteristics of metallated species . In the following, the influence of the substituents in the aryl group with respect to their positions and electronic nature is highlighted by means of absorption spectroscopy.…”

Section: Resultsmentioning

confidence: 61%

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Ruppel

Lungerich

Sturm

et al. 2020

Chemistry A European J

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Tetraaryltetrabenzoporphyrins (TATBPs) show, due to their optoelectronic properties, rising potential as dyes in various fields of physical and biomedical sciences. However, unlike in the case of porphyrins, the potential structural diversity of TATBPs has been explored only to little extent, owed mainly to synthetic hurdles. Herein, we prepared a comprehensive library of 30 TATBPs and investigated their fundamental properties. We elucidated structural properties by X‐ray crystallography and found explanations for physical properties such as solubility. Fundamental electronic aspects were studied by optical spectroscopy as well as by electrochemistry and brought in context to the stability of the molecules. Finally, we were able to develop a universal synthetic protocol, utilizing a readily established isoindole synthon, which gives TATBPs in high yields, regardless of the nature of the used arylaldehyde and without meticulous chromatographic purifications steps. This work serves as point of orientation for scientists, that aim to utilize these molecules in materials, nanotechnological, and biomedical applications.

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Section: Resultsmentioning

confidence: 61%

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

Ruppel

Lungerich

Sturm

et al. 2020

Chemistry A European J

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“…[39][40][41][42] For complex 1, its PL lifetime is 0.28 ms and EL lifetime is 0.9 ms (at a voltage of 12 V, Fig. 15,44 The short lifetime of complex 1 is caused by a much larger radiative decay rate (k r ) of 5.4 Â 10 4 s À1 , more than twice that of Pt-Ar 4 TBP (2.6 Â 10 4 s À1 ). 15,44 The short lifetime of complex 1 is caused by a much larger radiative decay rate (k r ) of 5.4 Â 10 4 s À1 , more than twice that of Pt-Ar 4 TBP (2.6 Â 10 4 s À1 ).…”

Section: Electroluminescent Propertiesmentioning

confidence: 99%

High-efficiency near-infrared organic light-emitting devices based on an iridium complex with negligible efficiency roll-off

et al. 2013

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For NIR-emitting organic light-emitting devices (OLEDs), platinum complexes have the record maximum external quantum efficiency (EQE), although such devices generally suffer from severe efficiency roll-off with increasing current densities. Here, we report on iridium complexes as a competent alternative for NIR dyes with high EQEs and negligible efficiency roll-off. A simple, charge-neutral iridium complex, iridium(III) bis(2-methyl-3-phenylbenzo[g]quinoxaline-N,C 0 ) acetylacetonate (Ir(mpbqx-g) 2 acac, 1), has been synthesized and characterized by a strong NIR emission with l max,peak at 777 nm and l max,shoulder at 850 nm in CH 2 Cl 2 solutions. The single-crystal and electronic structure as well as photophysical and electrochemical properties were systematically studied in comparison with its cationic counterpart [Ir(mpbqx-g) 2 (Bphen)] + PF 6 À (2, Bphen ¼ 4,7-diphenyl-1,10-phenanthroline). Complex 1 has seven times the quantum efficiency of complex 2 because of its much stronger spin-orbit coupling. NIR-emittingOLEDs based on complex 1 have been fabricated with a bipolar gallium complex as the host. The devices achieved a maximum EQE of up to 2.2% (J ¼ 13 mA cm À2 ) and a maximum radiant emittance (R max ) of 1.8 mW cm À2 . In particular, the EQEs remained around 2% over a wide range of current densities from 3 to 100 mA cm À2 . † Electronic supplementary information (ESI) available: The uncorrected PL spectra of complex 1 and complex 2 (Fig. S1); CV diagram for complex 1 and complex 2 (Fig. S2); the rst two triplet states for Ir(mpbqx-g) 2 (acac) calculated from the TDDFT approach (Table S1); current density vs. bias voltage characteristics and radiant emittance vs. bias voltage characteristics for devices with the congurations as ITO/NPB (40 nm)/complex 1: Ga 2 (saph) 2 q 2 (20 wt% 40 nm)/Bphen (30, 45, 60 nm, respectively)/Mg: Ag (150 nm) (Fig. S3); electroluminescence transients of the OLEDs (ITO/NPB (40 nm)/complex 1: Ga 2 (saph) 2 q 2 (20 wt% 40 nm)/Bphen (45 nm)/Mg: Ag (150 nm)) at 12 V (Fig. S4); the detailed structural data for the single crystal of complex 1 (Tables S2-S5); the complete author list of ref. 30 (PDF). See

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“…2,4 These chromophores are characterized by strong and narrow absorption bands in the red spectral region 6,29,30 and form brightly phosphorescent complexes with Pd and Pt 31−35 that are of interest for OLED and imaging applications. In contrast, asymmetrically π-extended porphyrins, which also have been known for a long time, 36−47 have been studied only occasionally.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Phosphorescent Asymmetrically π-Extended Porphyrins for Two-Photon Applications

Esipova

Vinogradov

2014

J. Org. Chem.

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Significant effort has been directed in recent years toward porphyrins with enhanced two-photon absorption (2PA). However, the properties of their triplet states, which are central to many applications, have rarely been examined in parallel. Here we report the synthesis of asymmetrically π-extended platinum(II) and palladium(II) porphyrins, whose 2PA into single-photon-absorbing states is enhanced as a result of the broken center-of-inversion symmetry and whose triplet states can be monitored by room-temperature phosphorescence. 5,15-Diaryl-syn-dibenzoporphyrins (DBPs) and syn-dinaphthoporphyrins (DNPs) were synthesized by [2 + 2] condensation of the corresponding dipyrromethanes and subsequent oxidative aromatization. Butoxycarbonyl groups on the meso-aryl rings render these porphyrins well-soluble in a range of organic solvents, while 5,15-meso-aryl substitution causes minimal nonplanar distortion of the macrocycle, ensuring high triplet emissivity. A syn-DBP bearing four alkoxycarbonyl groups in the benzo rings and possessing a large static dipole moment was also synthesized. Photophysical properties (2PA brightness and phosphorescence quantum yields and lifetimes) of the new porphyrins were measured, and their ground-state structures were determined by DFT calculations and/or X-ray analysis. The developed synthetic methods should facilitate the construction of π-extended porphyrins for applications requiring high two-photon triplet action cross sections.

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Photophysical Properties of Near-Infrared Phosphorescent π-Extended Platinum Porphyrins

Cited by 150 publications

References 37 publications

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

A Comprehensive Study on Tetraaryltetrabenzoporphyrins

High-efficiency near-infrared organic light-emitting devices based on an iridium complex with negligible efficiency roll-off

Synthesis of Phosphorescent Asymmetrically π-Extended Porphyrins for Two-Photon Applications

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