Synthesis of Direct β‐to‐β Linked Porphyrin Arrays with Large Electronic Interactions: Branched and Cyclic Oligomers

Cai, Hao; Fujimoto, Keisuke; Lim, Jong Min; Wang, Chaojie; Huang, Weiming; Rao, Yutao; Zhang, Senmiao; Shi, Hui; Yin, Bangshao; Chen, Bin; Ma, Ming; Song, Jianxin; Kim, Dongho; Osuka, Atsuhiro

doi:10.1002/anie.201407032

Cited by 37 publications

(18 citation statements)

References 35 publications

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“…This splitting possibly results from a strong excitonic coupling5 between NiPor and the corrole that originates from electronic perturbation of individual chromophores, after the direct meso–meso linkage is formed. It may also be due to the sterically hindered porphyrin substituents on the corrole ring 23. The difference in energy between the split Soret band and the unshifted Soret band (i.e., the excitonic coupling energy) is higher than that of both 10,10′‐corrole dimer 1 10c and corrole‐porphyrin‐corrole trimer 7 14a reported by Gryko and co‐workers and our group, respectively, but unlike to that of the recently reported 5,5′‐corrole dimer 4 11.…”

Section: Methodsmentioning

confidence: 99%

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First Example of a Modular Porphyrinoid Assembly Capable of Stabilizing Different Metal Ions in a Single Molecular Scaffold

Murugavel

Reddy

Dey

et al. 2015

Chemistry A European J

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We report the synthesis and characterization of porphyrin-corrole-porphyrin (Por-Cor-Por) hybrids directly linked at the meso-meso positions for the first time. The stability and solubility of the trimer are carefully balanced by adding electron-withdrawing substituents to the corrole ring and sterically bulky groups on the porphyrins. The new hybrids are capable of stabilizing more than one metal ion in a single molecular scaffold. The versatility of the triad has been demonstrated by successfully stabilizing homo- (Ni) and heterotrinuclear (Ni-Cu-Ni) coordination motifs. The solid-state structure of the NiPor-CuCor-PorNi hybrid was revealed by single-crystal X-ray diffraction studies. The Ni(II) porphyrins are significantly ruffled and tilted by 83° from the plane of corrole. The robustness of the synthesized hybrids was reflected in the electrochemical investigations and the redox behaviour of the hybrids show that the oxidation processes are mostly corrole-centred. In particular it is worth noting that the Por-Cor-Por hybrid can further be manipulated due to the presence of substituent-free meso-positions on both the terminals.

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Section: Methodsmentioning

confidence: 99%

“…It may also be due to the sterically hinderedp orphyrin substituents on the corrole ring. [23] The difference in energy between the split Soret band and the unshifted Soret band (i.e., the excitonic coupling energy) is highert han that of both Figure 3. X-ray crystal structure of 8b (3,5-di-tert-butyl and hydrogens are omittedf or clarity).…”

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confidence: 86%

First Example of a Modular Porphyrinoid Assembly Capable of Stabilizing Different Metal Ions in a Single Molecular Scaffold

Murugavel

Reddy

Dey

et al. 2015

Chemistry A European J

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“…Recently we explored various porphyrinoids by using Suzuki-Miyaura coupling. Reported examples include cyclic porphyrin rings, BODIPY-porphyrin hybrids, and earring porphyrins [24][25][26][27][28] . Despite of these studies, we thought that this coupling strategy could be applied to the synthesis of pyridine-incorporated expanded porphyrins.…”

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confidence: 99%

Benzene- and pyridine-incorporated octaphyrins with different coordination modes toward two PdII centers

Liu

Zhang

et al. 2020

Nat Commun

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Expanded porphyrins have received considerable attention due to their unique optical, electrochemical and coordination properties. Here, we report benzene- and pyridine-incorporated octaphyrins(1.1.0.0.1.1.0.0), which are synthesized through Suzuki-Miyaura coupling of α,α′-diboryltripyrrane with m-dibromobenzene and 2,6-dibromopyridine, respectively, and subsequent oxidation with 2,3-dicyano-5,6-dichlorobenzoquinone. Both octaphyrins are nonaromatic and take on dumbbell structures. Upon treatment with Pd(OOCCH3)2, the benzene-incorporated one gives a Ci symmetric NNNC coordinated bis-PdII complex but the pyridine incorporated one gives Ci and Cs symmetric NNNC coordinated bis-PdII complexes along with an NNNN coordinated bis-PdII complex bearing a transannular C–C bond between the pyrrole α-positions. In addition, these two pyridine-containing NNNC PdII complexes undergo trifluoroacetic acid-induced clean interconversion.

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“…Diboryltripyrrane 1 was synthesized through Ir‐catalyzed borylation of a tripyrrane precursor . β,β′‐dibromo Ni II porphyrin 2 a was synthesized as previously reported . With 1 and 2 a in hand, 4 a was prepared smoothly through the Suzuki–Miyaura reaction (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

π‐Extended “Earring” Porphyrins with Multiple Cavities and Near‐Infrared Absorption

et al. 2016

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β,β-tripyrrin-bridged earring porphyrins were synthesized through Suzuki-Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x-ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near-infrared (NIR) absorptions and metal insertion leads to red-shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties.

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Synthesis of Direct β‐to‐β Linked Porphyrin Arrays with Large Electronic Interactions: Branched and Cyclic Oligomers

Cited by 37 publications

References 35 publications

First Example of a Modular Porphyrinoid Assembly Capable of Stabilizing Different Metal Ions in a Single Molecular Scaffold

First Example of a Modular Porphyrinoid Assembly Capable of Stabilizing Different Metal Ions in a Single Molecular Scaffold

Benzene- and pyridine-incorporated octaphyrins with different coordination modes toward two PdII centers

π‐Extended “Earring” Porphyrins with Multiple Cavities and Near‐Infrared Absorption

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