Singly N‐Confused [26]Hexaphyrin: A Binucleating Porphyrinoid Ligand for Mixed Metals in Different Oxidation States

Gokulnath, Sabapathi; Yamaguchi, Kazuya; Toganoh, Motoki; Mori, Shigeki; Uno, Hidemitsu; Furuta, Hiroyuki

doi:10.1002/ange.201006784

Cited by 18 publications

(7 citation statements)

References 38 publications

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“…385 Singly N-confused hexaphyrins were obtained by reacting N-confused tripyrrane dicarbinol 804 with tripyrrane 825 in the presence of boron trifluoride etherate, followed by oxidation with DDQ (Scheme 264). 386 Two oxo products were generated, aromatic N-confused hexaphyrin 826 (23%) and the antiaromatic reduced form 827 (11%). Reaction of 826 with AuCl•SMe 2 gave the gold(III) derivative 828, and this could be converted into the mixed gold(III)−platinum(II) derivative 829.…”

Section: Expanded Porphyrinoids With Inverted Pyrrole Rings That Rese...mentioning

confidence: 99%

Carbaporphyrinoid Systems

2016

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Following immediately after the serendipitous discovery of N-confused porphyrins, remarkably diverse carbaporphyrinoid systems have been synthesized and investigated. By replacing a pyrrolic unit within the porphyrin framework with cyclopentadiene, indene, azulene, cycloheptatriene, or benzene, new families of porphyrin-like macrocycles were produced. True carbaporphyrins are fully aromatic structures, while benziporphyrins are essentially devoid of macrocyclic aromatic character, and azuliporphyrins fall midway between the two extremes. Monocarbaporphyrinoids are superior organometallic ligands and form stable complexes with copper(III), silver(III), gold(III), nickel(II), palladium(II), platinum(II), rhodium(III), iridium(III), and ruthenium(II). Unusual oxidation reactions have also been discovered, commonly leading to derivatization of the internal carbon atom. In addition, structural rearrangements have been uncovered that allow the conversion of azuliporphyrins into benzocarbaporphyrins, and benziporphyrins into carbaporphyrins. Although less well studied, many examples of dicarbaporphyrinoids have been reported, and these show equally intriguing characteristics. Furthermore, contracted and expanded carbaporphyrinoids have been investigated. Studies in this area provide fundamental insights into the aromatic properties, tautomerization, and reactivity of porphyrins and related macrocyclic systems.

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Section: Expanded Porphyrinoids With Inverted Pyrrole Rings That Rese...mentioning

confidence: 99%

Carbaporphyrinoid Systems

2016

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“…Relative to the large amount of the N-confused and N-fused porphyrins, only a few N-inversions were reported in the literature so far. 16,20 In the present work, we theoretically designed some topologically different structures of the bismetalated [32]octaphyrins(1,0,1,0,1,0,1,0) (Scheme 1, the notation "H" and "M" denote the molecules with Huckel and Mobius topologies, respectively). There are six intermediates along the isomerization pathway, called 1-H, 2-M, 3-M, 4-H, 5-M, and 6-H. Pyrroles A and E are two inverted rings in the initial Huckel-type 1-H.…”

Section: Introductionmentioning

confidence: 99%

Chiral Interconversions of Pd and/or Au Bis-Metalated [32]Octaphyrins(1,0,1,0,1,0,1,0) Involving Hückel and Möbius Macrocyclic Topologies: A Theoretical Prediction

Liu

Tian

et al. 2012

J. Org. Chem.

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Several Pd and/or Au bis-metalated [32]octaphyrins(1,0,1,0,1,0,1,0) were theoretically designed with rich conformations of Hückel or Möbius topology. The conformations and hence properties of macrocycles were tuned by twisting the active pyrrolic ring either clockwise (through multistep reactions with several Hückel and Möbius macrocyclic intermediates) or anticlockwise (via a direct Hückel-Hückel chiral interconversion). The encapsulated metal atoms, M(1), M(2) = Pd, Au, give different impacts on these two reaction processes. Facile occurrences of chiral interconversions between two enantiomers of bis-metalated octaphyrins were predicted with the largest activation barrier less than 40 kcal/mol. Some Au-coordinated octaphyrins (M(1) = Au) were demonstrated to be thermodynamically stable with large negative nucleus-independent chemical shift (NICS) values, which are comparable to those of the synthetic Pd-coordinated complexes. The free-base [32]octaphyrins(1,0,1,0,1,0,1,0) display the characteristic absorption spectra with distinct sharp Soret-like bands. After metalation, the Soret-like bands are red-shifted in different degrees along with the appearance of rather weak Q-like band. The heterometal-coordinated complexes (i.e., M(1) ≠ M(2)) show stronger and more splitting absorptions than the homometal-coordinated ones with M(1) = M(2). The hyperpolarizabilities sharply augment with the metalation in Hückel systems due to the destruction of the centrosymmetry and the increase in polarizability by coordinated metal atoms.

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“…259 Especially, singly N-confused [26]hexaphyrin was even able to coordinate with two different metal ions in variable oxidation states. 260 Besides, expanded N-confused porphyrins show attractive light absorption/emission properties such as NIR fluorescence emission. Considering these characteristics, expanded N-confused porphyrins are promising candidates suitable for designing NIR chemosensors that can avoid biological autofluorescence and eliminate biological damage.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Development of Ion Chemosensors Based on Porphyrin Analogues

2016

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Sensing of metal ions and anions is of great importance because of their widespread distribution in environmental systems and biological processes. Colorimetric and fluorescent chemosensors based on organic molecular species have been demonstrated to be effective for the detection of various ions and possess the significant advantages of low cost, high sensitivity, and convenient implementation. Of the available classes of organic molecules, porphyrin analogues possess inherently many advantageous features, making them suitable for the design of ion chemosensors, with the targeted sensing behavior achieved and easily modulated based on their following characteristics: (1) NH moieties properly disposed for binding of anions through cooperative hydrogen-bonding interactions; (2) multiple pyrrolic N atoms or other heteroatoms for selectively chelating metal ions; (3) variability of macrocycle size and peripheral substitution for modulation of ion selectivity and sensitivity; and (4) tunable near-infrared emission and good biocompatibility. In this Review, design strategies, sensing mechanisms, and sensing performance of ion chemosensors based on porphyrin analogues are described by use of extensive examples. Ion chemosensors based on normal porphyrins and linear oligopyrroles are also briefly described. This Review provides valuable information for researchers of related areas and thus may inspire the development of more practical and effective approaches for designing high-performance ion chemosensors based on porphyrin analogues and other relevant compounds.

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Singly N‐Confused [26]Hexaphyrin: A Binucleating Porphyrinoid Ligand for Mixed Metals in Different Oxidation States

Cited by 18 publications

References 38 publications

Carbaporphyrinoid Systems

Carbaporphyrinoid Systems

Chiral Interconversions of Pd and/or Au Bis-Metalated [32]Octaphyrins(1,0,1,0,1,0,1,0) Involving Hückel and Möbius Macrocyclic Topologies: A Theoretical Prediction

Development of Ion Chemosensors Based on Porphyrin Analogues

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