Bimetallic Figure‐Eight Octaphyrins Split into Four‐Pyrrolic Macrocycles

Latos‐Grażyński, Lechosław

doi:10.1002/anie.200460645

Cited by 39 publications

(14 citation statements)

References 33 publications

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“…85,86 Beside these, the meso-aryl expanded porphyrins are quite interesting from the viewpoint of mutual chemical interconversions (metamorphosis). 87,88 The most remarkable example is the efficient and quantitative splitting reaction of bis-Cu(II) complex of a [36]octaphyrin into two molecules of Cu(II) porphyrins upon heating. 89 This transformation requires the rapture and formation of two carboncarbon double bonds in a metathesis manner.…”

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confidence: 99%

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Osuka

Tsurumaki

Tanaka

2011

Bulletin of the Chemical Society of Japan

120

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After a brief survey of our efforts in the development of novel porphyrinoids that include mesomeso-linked porphyrin arrays, meso-aryl expanded porphyrins, and transition-metal-catalyzed functionalizations of porphyrins, a particular focus in this account is placed on the chemistry of subporphyrins that has been explored in our group. Subporphyrin is a legitimate ring-contracted porphyrin consisting of three pyrrolic subunits domed in a C 3 symmetric bowl shape. While subporphyrins are simple and small macrocycles and possess a key position in porphyrin chemistry, they had been elusive until our first synthesis of tribenzosubporphines in 2006. Shortly after, synthetic protocols of mesoaryl-substituted subporphyrins were developed to produce various subporphyrins with versatile electronic properties that can be widely tuned by meso-aryl substituents. Raney nickel reduction was used to prepare meso-alkyl-substituted subporphyrins from meso-thienyl-substituted subporphyrins. Subchlorins and subbacteriochlorins were prepared respectively by the reduction of subporphyrins with p-tosylhydrazide and Raney nickel. While subporphyrins and subchlorins share conjugated 14³-electronic circuits, subbacteriochlorins have a rare [13]diazaannulene circuit maintained through the lone-pair electrons of the nitrogen atom. The aromaticity decreases in the order of subporphyrin > subchlorin > subbacteriochlorin, as indicated from 1 H-and 11 B NMR spectra and nuclear independent chemical shift (NICS) calculations. Despite these progresses, the chemistry of subporphyrins is still in the infant stage with many untouched aspects and further improvements in synthetic yields are highly desirable for the developments of the chemistry of subporphyrins as well as their applications in diverse fields. A Brief Survey of Our Efforts in the Exploration of Novel PorphyrinoidsIn the last three decades, we have been involved in the exploration of novel porphyrinoids with intriguing structures, electronic and optical properties, and functions. We entered porphyrin chemistry with the aim to synthesize covalently linked organic constructs that can mimic the whole excitation energy transfer and electron transfer events of the photosynthetic reaction centers within a single molecular entity. 13 In the course of these studies, we fortunately encountered new reactions and structures, which drove us to change our research style from a well-designed, goal-orientated path to a flexible discovery-searching strategy to explore novel porphyrinoids. By following the flexible research style, we have explored mesomeso-linked Zn(II) porphyrin arrays, meso-aryl expanded porphyrins, transition-metal-catalyzed porphyrin modifications, and subporphyrins. After a brief survey of the former three topics, a particular focus is placed on the chemistry of subporphyrins that are legitimate ring-contracted porphyrins. As described below, subporphyrins are a new class of functional molecules, particularly in view of their highly tunable electronic and optical properties.

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confidence: 99%

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Osuka

Tsurumaki

Tanaka

2011

Bulletin of the Chemical Society of Japan

120

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“…[6] In addition, skeletal rearrangements and the resulting intriguing chemical reactivities, which are often triggered upon metalation have been studied. [7] In 2003, Vogel et al found that metalation of 5,24-dioxo-octaphyrin(1.1.1.0.1.1.1.0) with nickel(II) caused a rearrangement to give a bis-nickel(II) complex of spirodicorrole through the extrusion of two carbon dioxide molecules. [8] They also disclosed that the metalation of [34]octaphyrin(1.1.1.0.1.1.1.0) with palladium(II) caused a rearrangement to a bis-spirodiporphyrin skeleton.…”

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Boron(III) Induced Skeletal Rearrangement of Hexaphyrin(1.1.1.1.1.1) to Hexaphyrin(2.1.1.0.1.1)

2010

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“…Octaphyrin (1.1.1.1.1.1.0.0) ( OP ), being a conjugated π system may be the excellent candidate for the materials science. Many research groups have reported the synthesis and structural properties of isomers of Octaphyrin (1.1.1.1.1.1.0.0) (Franck and Nonn, 1995; Latos-Grazynski, 2004; Shimizu et al, 2005; Rath et al, 2005b; Geffroy et al, 2006; Hiroto et al, 2006; Kumar et al, 2007; Misra and Chandrashekar, 2008; Anaka et al, 2011; Sasabe and Kido, 2011, 2013a,b; Mori et al, 2012a; Jin and Tang, 2013; Kido et al, 2013; Naoda and Osuka, 2014; Sekine et al, 2014; Islam and Pandith, 2014a; Anguera et al, 2015; Romain et al, 2015). According to Chandershaker et al the core-modified expanded porphyrins containing 26, 36, and 54 π electrons because of their exceptionally massive two-photon absorption cross- sections may be considered among the most effective appropriate candidates, particularly as organic NLO materials (Pushpan and Chandrashekar, 2002).…”

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confidence: 99%

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

Islam

Lone²

2017

Front. Chem.

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The electronic and nonlinear optical (NLO) properties of octaphyrin derivatives were studied by employing the DFT/TDFT at CAM-B3LYP/6-311++G (2d, 2p) level of the theory. Thiophene, phenyl, methyl and cyano moieties were substituted on the molecular framework of octaphyrin core, in order to observe the change in optoelectronic and nonlinear response of these systems. The frontier molecular orbital studies and values of electron affinity reveals that the studied compounds are stable against the oxygen and moisture present in air. The calculated ionization energies, adiabatic electron affinity and reorganization energy values indicate that octaphyrin derivatives can be employed as effective n-type material for Organic Light Emitting Diodes (OLEDs). This character shows an enhancement with the introduction of an electron withdrawing group in the octaphyrin framework. The polarizability and hyperpolarizability values of octaphyrin derivatives demonstrate that they are good candidates for NLO devices. The nonlinear response of these systems shows enhancement on the introduction of electron donating groups on octaphyrin moiety. However, these claims needs further experimental verification.

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Bimetallic Figure‐Eight Octaphyrins Split into Four‐Pyrrolic Macrocycles

Cited by 39 publications

References 33 publications

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Boron(III) Induced Skeletal Rearrangement of Hexaphyrin(1.1.1.1.1.1) to Hexaphyrin(2.1.1.0.1.1)

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

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