One‐Pot Synthesis of a bis‐Pocket Corrole through a 14‐fold Bromination Reaction

Norheim, Hans-Kristian; Schneider, Christian; Gagnon, Kevin J.; Ghosh, Abhik

doi:10.1002/open.201600168

Cited by 3 publications

(4 citation statements)

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“…Synthesis of phenol-and resorcinol-appended metallocorroles. Rhenium-oxo [48][49][50][51][52][53] and gold [54][55][56][57][58][59][60][61][62][63] tris(4-methoxyphenyl)corrole, M[TpOMePC] (M = ReO, Au), and tris(3,5-dimethoxyphenyl)corrole, M[T(3,5-OMe)PC] (M = ReO, Au), which rank among the most readily accessible 5d metallocorroles [64][65][66][67][68][69] , were used as starting materials. The choice of the two metals was dictated by the fact that they yield rugged, electronically innocent complexes that have been shown to act as triplet photosensitizers in oxygen sensing and in vitro photodynamic therapy experiments.…”

Section: Resultsmentioning

confidence: 99%

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Phenol- and resorcinol-appended metallocorroles and their derivatization with fluorous tags

Alemayehu

Ghosh

2022

Sci Rep

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Boron tribromide-mediated demethylation of rhenium-oxo and gold meso-tris(4-methoxyphenyl)corrole and meso-tris(3,5-dimethoxyphenylcorrole), M[TpOMePC] and M[T(3,5-OMe)PC] (M = ReO, Au), have yielded the corresponding phenol- and resorcinol-appended metallocorroles, M[TpOHPC] and M[T(3,5-OH)PC], in good yields. The latter compounds proved insoluble in dichloromethane and chloroform but soluble in THF. The M[T(3,5-OH)PC] derivatives also proved moderately soluble in 0.05 M aqueous KOH. Unlike oxidation-prone aminophenyl-substituted corroles, the phenol- and resorcinol-appended metallocorroles could be readily handled in air without special precautions. The phenolic metallocorroles could be readily alkylated with 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl iodide (“FtI”) to afford the fluorous-tagged metallocorroles M[TpOFtPC] and M[T(3,5-OFt)PC] in > 90% yields. The simplicity of the synthetic protocols promise a wide range of phenolic and fluorous-tagged porphyrin analogues with potential applications to diverse fields such as sensors, catalysis, and photodynamic therapy, among others.

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Section: Resultsmentioning

confidence: 99%

“…Silica gel 60 (0.04–0.063 mm particle size, 230–400 mesh) was employed for flash chromatography. Metallocorrole starting materials were prepared as previously described 48 , 56 , 60 .…”

Section: Methodsmentioning

confidence: 99%

Phenol- and resorcinol-appended metallocorroles and their derivatization with fluorous tags

Alemayehu

Ghosh

2022

Sci Rep

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“…58 A considerable nonplanar macrocycle conformation results from the introduction of sterically hindered substituents at the β-positions. 41,59,60 While irradiating with a high-intensity laser, the functionalized porphyrins display large σ 2PA , high nonlinearities, and quick optical response. 61,62 However, such reports on corroles are limited.…”

Section: ■ Introductionmentioning

confidence: 99%

“…β-Formylcorroles showed intriguing photophysical and redox properties. ,− Additionally, β-bromo-substituted triarylcorroles are effective precursors for nucleophilic aromatic substitutions and also Pd-catalyzed cross-coupling reactions using aryl/alkyboronic acids and organotin reagents. − Studies on push–pull or mixed β-substituted corroles are scarce due to synthetic difficulty . A considerable nonplanar macrocycle conformation results from the introduction of sterically hindered substituents at the β-positions. ,, While irradiating with a high-intensity laser, the functionalized porphyrins display large σ 2PA , high nonlinearities, and quick optical response. , However, such reports on corroles are limited.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Dynamics and Strong Two-Photon Absorption Properties of Nonplanar β-Functionalized “Push–Pull” Copper Corroles with a Mixed Substituent Pattern

et al. 2022

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A new series of nonplanar and unsymmetrically βfunctionalized "push−pull" copper corroles, CuTPC(CHO)R 7 [R = H, Br, Ph, Me, or 2-thienyl (Th)], were synthesized and characterized to elucidate the effect of β-functionalization and nonplanarity on the photophysical, redox, and nonlinear optical (NLO) properties on the corrole ring. The synthetic route to unsymmetrically β-octasubstituted copper corroles includes bromination of CuTPC(CHO) to get CuTPC(CHO)Br 7 in 80% yield, which was further subjected to the Pd-catalyzed Suzuki reaction. CuTPC(CHO)Br 7 exhibited a large red shift in the Soret band (Δλ max = 35−40 nm) and both the Q bands (Δλ max = 10−50 nm), as compared to CuTPC and CuTPC(CHO). CuTPC(CHO)Br 7 was 510 and 290 mV anodically shifted in the first oxidation and the first reduction compared to CuTPC owing to the strong −I effect of CHO and Br groups. Density functional theory studies revealed that all the β-octasubstituted copper corroles exhibited highly nonplanar saddle-shape conformation of the corrole ring. Very high torsional saddling was observed for CuTPC(CHO)Th 7 (79−83°) than that for CuTPC (49−53°), even larger than that for CuTPCBr 8 (67−70°). Femtosecond laser-induced third-order NLO studies from these copper corroles showed strong twophoton absorption cross-sections (0.48−6.98 × 10 4 GM) and self-focusing-type positive nonlinear refraction behavior. The observed structure-dependent two-photon absorption coefficients (β) are in the range of ∼2.7−20.9 × 10 −12 m/W, and the n 2 values are in the range of ∼0.64−6.45 × 10 −18 m 2 /W. The present results may facilitate a new window for these copper corroles in nonlinear optical devices, femtosecond optical limiters, and many other ultrafast photonic applications.

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Metal complexes of corrole

Nardis

Mandoj

Stefanelli

et al. 2019

Coordination Chemistry Reviews

141

120

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One‐Pot Synthesis of a bis‐Pocket Corrole through a 14‐fold Bromination Reaction

Cited by 3 publications

References 42 publications

Phenol- and resorcinol-appended metallocorroles and their derivatization with fluorous tags

Phenol- and resorcinol-appended metallocorroles and their derivatization with fluorous tags

Ultrafast Dynamics and Strong Two-Photon Absorption Properties of Nonplanar β-Functionalized “Push–Pull” Copper Corroles with a Mixed Substituent Pattern

Metal complexes of corrole

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