Helicity Induction and Two-Photon Absorbance Enhancement in Zinc(II) Meso−Meso Linked Porphyrin Oligomers via Intermolecular Hydrogen Bonding Interactions

Yoon, Zin Seok; Park, Soo‐Jin; Inoue, Hidenari; Kim, Dongho; Osuka, Atsuhiro

doi:10.1021/ja043428x

Cited by 69 publications

(52 citation statements)

References 21 publications

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“…6 It is amazing that extremely long porphyrin arrays (even 128-mer and 256-mer) smoothly undergo the coupling reaction, although they bear only two edge free meso-positions that can be used for the coupling. On the basis of this coupling reaction, we prepared extremely long porphyrin arrays up to linear 1024-mer, 6 three-dimensionally extending windmill porphyrin arrays, 79 dihedral angle controlled mesomeso-linked diporphyrins, 10,11 large porphyrin wheels, 1214 helical porphyrin arrays held by intermolecular hydrogen bonding hostguest interaction, 15 and directly linked porphyrin rings. 16 mesomeso-Linked diporphyrin motifs are suitable for supramolecular assembling.…”

Section: A Brief Survey Of Our Efforts In the Exploration Of Novel Pomentioning

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

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122

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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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Section: A Brief Survey Of Our Efforts In the Exploration Of Novel Pomentioning

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

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122

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“…In the last decade, we have explored a variety of porphyrin arrays on the basis of Ag(I)-promoted oxidative mesomeso coupling reaction of 5,15-diaryl Zn(II)porphyrin, 19 which include extremely long linear arrays, 2 helical arrays, 3 threedimensional windmill arrays, 4 cyclic arrays, 5 supramolecular porphyrin boxes, 6 highly conjugated porphyrin tapes, 7 and an antiaromatic porphyrin sheet. 8 As such, this simple synthetic method that allows a direct porphyrinporphyrin connection has been demonstrated quite useful for construction of novel multiporphyrinic architectures of attractive properties and functions.…”

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confidence: 99%

Directly Linked Corrole Oligomers via Facile Oxidative 3–3′ Coupling Reaction

Hirabayashi

Omote

Aratani

et al. 2012

Bulletin of the Chemical Society of Japan

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Upon heating with p-chloranil in CHCl 3 , 5,10,15-tris(pentafluorophenyl)corrole (1H) underwent regioselective oxidative coupling reaction at the 3,3¤-position to give dimer 2H and trimer 3H. Oxidation of 2H with p-fluoranil gave tetramer 4H and hexamer 6H. The crystal structures have been revealed for 2H, cobalt(III) complexed trimer 3Co¢py 6 , and tetramer 4Co¢py 8 .In the last decade, we have explored a variety of porphyrin arrays on the basis of Ag(I)-promoted oxidative mesomeso coupling reaction of 5,15-diaryl Zn(II)porphyrin, 19 which include extremely long linear arrays, 2 helical arrays, 3 threedimensional windmill arrays, 4 cyclic arrays, 5 supramolecular porphyrin boxes, 6 highly conjugated porphyrin tapes, 7 and an antiaromatic porphyrin sheet. 8 As such, this simple synthetic method that allows a direct porphyrinporphyrin connection has been demonstrated quite useful for construction of novel multiporphyrinic architectures of attractive properties and functions. 9A similar synthetic method that permits a direct corrole corrole linkage should have analogous synthetic potentials and thus be highly desirable. Corrole, a one-meso-carbon-contracted porphyrin analogue bearing a direct pyrrolepyrrole linkage, is a unique 18³ aromatic macrocycle stabilizing higher oxidation states of some metal ions.10 The chemistry of corroles has recently been boosted by the development of facile synthetic methods of 5,10,15-triaryl-substituted corroles, 1113 but still remains rather unexplored as compared to those of porphyrins. In particular, studies on covalently linked corrole oligomers have been limited compared with an extensive lineup of porphyrin counterparts. Guilard et al. reported a series of face-to-face porphyrincorrole hybrids as well as corrole dimers as a promising model of a four-electron reduction catalyst of oxygen to water, 14 and Smith et al. reported aromatic-bridged corrole dimers and corroleporphyrin hybrids.15 Gross et al. reported that directly 3,3¤-linked corrole dimers 2a and 2b were formed during the metalation of 5,10,15-tris(pentafluorophenyl)corrole 1H with Co(OAc) 2 and triphenylphosphine or Cu(OAc) 2 ¢H 2 O (Chart 1).16 Cavaleiro et al. found that corrole free base 1H underwent oxidative coupling reaction in a low yield. 17 We explored a rational synthetic route to doubly ¢,¢-linked corrole dimers through a singly 2,2¤-linked corrole dimer on the basis of Pd-catalyzed oxidative coupling reaction of 2-borylated corrole followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).18 Quite unexpectedly, an oxidized form of doubly ¢,¢-linked corrole dimer exists as a neutral biradical that is stable under air and water.Here, we wish to report a very simple yet effective synthetic method for direct coupling of 1H. Results and DiscussionCorrole 1H has been most frequently used, due to its easy availability and chemical stability. Synthesis of 1H has been achieved by solvent-free protocols 11,19 or via a dipyrromethane route 13 and a tetrapyrrane route. 20 In all these procedures, ...

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“…13 Based on the following experiments including steady-state absorption and emission, and time resolved fluorescence spectroscopy as well, we could provide some evidences on the improved conformational homogeneity. By reducing the conformational heterogeneity, the formation of helical arrays has also allowed the enhanced nonlinear optical response probed by femtosecond Z-scan technique.…”

Section: Introductionmentioning

confidence: 94%

Zn(II)porphyrin Helical Arrays: A Strategy to Overcome Conformational Heterogeneity by Host-Guest Chemistry

Yoon

Easwaramoorthi

Kim

2008

Bulletin of the Korean Chemical Society

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Conformational heterogeneity of directly linked multiporphyrin arrays with larger molecular length retards their utilities in practical applications such as two-photon absorption and molecular photonic wire. In this regard, here we adopted a way to overcome the conformational heterogeneity through hydrogen bonding by selective binding of meso aryl substituents of porphyrins (host) with urea (guest) to form helical structure. Using steady-state and time-resolved spectroscopy, we observed the enhanced fluorescence quantum yield bỹ 1.8 to 2.4 times, enhanced anisotropy values and the disappearance of fast fluorescence decay component in the host-guest helical forms. In addition, the enhanced nonlinear optical responses of helical arrays infer the extended inter-porphyrin electronic coupling due to a significant change in dihedral angle between the neighboring porphyrin moieties. The current host-guest strategy will provide a guideline to improve the structural homogeneity of the photonic wire.

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Helicity Induction and Two-Photon Absorbance Enhancement in Zinc(II) Meso−Meso Linked Porphyrin Oligomers via Intermolecular Hydrogen Bonding Interactions

Abstract: Helicity has been induced in meso-meso linked oligomers by hydrogen bonding host-guest interactions with cyclic urea. Helical porphyrin arrays thus formed exhibit chirality amplification and enhanced two-photon absorption properties.

Cited by 69 publications

References 21 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

Directly Linked Corrole Oligomers via Facile Oxidative 3–3′ Coupling Reaction

Zn(II)porphyrin Helical Arrays: A Strategy to Overcome Conformational Heterogeneity by Host-Guest Chemistry

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