Synthesis of BODIPY‐Appended Subporphyrins

Sugimoto, Hisashi; Muto, Masahiro; Tanaka, Takayuki; Osuka, Atsuhiro

doi:10.1002/ejoc.201001188

Cited by 21 publications

(23 citation statements)

References 30 publications

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“…Polyads exhibiting 1 Bodipy*→porphyrin processes is well documented . In order to explain this fast rate for 1 Bodipy*→porphyrin in P 2 B 2 Q , comparisons with some literature examples are provided (Figure : D1 , D2 , D3 , D4 , D5 , D6 , D7 , D8 , D9 , D10 , D11 , D12 , and D13 .…”

Section: Resultsmentioning

confidence: 99%

Azophenine as Central Core for Efficient Light Harvesting Devices

Karsenti

Harvey

2018

ChemPhysChem

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The notoriously non-luminescent uncycled azophenine (Q) was harnessed with Bodipy and zinc(II)porphyrin antennas to probe its fluorescence properties, its ability to act as a singlet excited state energy acceptor and to mediate the transfer. Two near-IR emissions are depicted from time-resolved fluorescence spectroscopy, which are most likely due to the presence of tautomers of very similar calculated total energies (350 cm ; DFT; B3LYP). The rates for energy transfer, k (S ), for Bodipy*→Q are in the order of 10 -10 s and are surprisingly fast when considering the low absorptivity properties of the lowest energy charge transfer excited state of azophenine. The rational is provided by the calculated frontier molecular orbitals (MOs) which show atomic contributions in the C H C≡CC H arms, thus favoring the double electron exchange mechanism. In the mixed-antenna Bodipy-porphyrin star molecule, the rate for Bodipy*→porphyrin has also been evaluated (≈16×10 s ) and is among the fastest rates reported for Bodipy-zinc(II)porphyrin pairs. This astonishing result is again explained from the atomic contributions of the C H C≡CC H and C≡CC H arms thus favouring the Dexter process. Here, for the first time, this process is found to be sensitively temperature-dependent. The azophenine turns out to be excellent for electronic communication.

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Section: Resultsmentioning

confidence: 99%

Azophenine as Central Core for Efficient Light Harvesting Devices

Karsenti

Harvey

2018

ChemPhysChem

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“…151 BODIPYsubporphyrin hybrids bridged by a 1,4-biphenylene or 1,4-diphenylethynylene spacer were synthesized either by palladium-catalyzed SuzukiMiyaura reaction or Sonogashira reaction (Figure 10). 152 In all cases, intramolecular excitation energy transfer from the subporphyrin core to the BODIPY peripheries is efficient, but the fluorescence intensity of the BODIPY segments is found to depend upon the presence or absence of ¢-methyl groups of the BODIPY subunit. Ferrocene-appended subporphyrins 40 and 41 were prepared by conventional acid-catalyzed condensation and Suzuki Miyaura cross-coupling, respectively ( Figure 11).…”

Section: Award Accountsmentioning

confidence: 95%

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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“…Another class of BODIPY-porphyrinoids based on subporphyrins was developed by Osuka and coworkers. 209 BODIPY-subporphyrin hybrids bridged by a 1,4-biphenylene or 1,4-diphenylethynylene spacer (361-362 and 363-364, respectively; Fig. 84) were obtained via either the palladium-catalyzed Suzuki-Miyaura cross-coupling or Sonogashira cross-coupling.…”

Section: Oligomers and Polyads Incorporating Dpmmentioning

confidence: 99%

Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices

2014

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This review article presents the most recent developments in the use of materials based on dipyrromethene (DPM) and azadipyrromethenes (ADPM) for organic photovoltaic (OPV) applications. These chromophores and their corresponding BF2-chelated derivatives BODIPY and aza-BODIPY, respectively, are well known for fluorescence-based applications but are relatively new in the field of photovoltaic research. This review examines the variety of relevant designs, synthetic methodologies and photophysical studies related to materials that incorporate these porphyrinoid-related dyes in their architecture. The main idea is to inspire readers to explore new avenues in the design of next generation small-molecule and bulk-heterojunction solar cell (BHJSC) OPV materials based on DPM chromophores. The main concepts are briefly explained, along with the main challenges that are to be resolved in order to take full advantage of solar energy.

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Synthesis of BODIPY‐Appended Subporphyrins

Cited by 21 publications

References 30 publications

Azophenine as Central Core for Efficient Light Harvesting Devices

Azophenine as Central Core for Efficient Light Harvesting Devices

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

Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices

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