Synthesis and properties of group 15 element porphyrin peroxides

Satoh, Wataru; Masumoto, Shuji; Yamamoto, Yohsuke; Akiba, Kin‐ya

doi:10.1002/hc.1065

Cited by 17 publications

(13 citation statements)

References 38 publications

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“…Compound 205 reacted with triphenylphosphine via M3 to give 204‐OTf and triphenylphosphine oxide quantitatively and the reactivity was in the order of porphyrins of phosphorus > arsenic > stiborane (Eq. (92)) 142. …”

Section: Porphyrins Of Group 15 Elements (Phosphorus Arsenic and Anmentioning

confidence: 99%

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

Akiba¹

2011

Heteroatom Chemistry

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Section: Porphyrins Of Group 15 Elements (Phosphorus Arsenic and Anmentioning

confidence: 99%

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

Akiba¹

2011

Heteroatom Chemistry

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“…9−13 Axial bonding is another active mode of functionalizing that is distinctive of the main-group porphyrins. 2,6,14,15 These adaptable properties make them potential candidates for a range of applications which include artificial photosynthesis, 1,2,16−18 dye-sensitized solar cells, 18,19 molecular catalysis, 7,20,21 molecular electronics and photonics, 22−25 photodynamic therapy, 26−31 etc. Among the main-group porphyrins, group 15 porphyrins intrinsically possess very positive potentials.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The observed high potentials are due to the presence of Sb(+5) ion in the cavity and 30 fluorine atoms on the peripherals. The anodic scan of the antimony(V) porphyrins revealed the oxidation process at 2.20, 2.20, 2.16, 1.91, and 1.81 V vs SCE for SbT(4CF It is important to compare the current redox potentials with a literature compound, SbTPP(CH 3 )(F)•PF 6 , where fluorine is one of the axial ligands. 64 This compound showed the reduction processes at −0.38 and −0.83 V vs SCE and oxidation process at 1.75 V vs SCE in benzonitrile with 0.1 M tetrabutylammonium perchlorate.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Main-group porphyrins are one of the most versatile and fascinating molecules in the porphyrin family as they are highly photoactive, redox-rich, and possess flexible structural properties. − Notably, these properties can be tuned easily by incorporating a variety of main-group elements in the porphyrin cavity . Additionally, the photophysical and redox properties can be adjusted by functionalizing the porphyrin peripherals. − Axial bonding is another active mode of functionalizing that is distinctive of the main-group porphyrins. ,,, These adaptable properties make them potential candidates for a range of applications which include artificial photosynthesis, ,,− dye-sensitized solar cells, , molecular catalysis, ,, molecular electronics and photonics, − photodynamic therapy, − etc.…”

Section: Introductionmentioning

confidence: 99%

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Fluorinated Antimony(V) Tetraarylporphyrins as High-Valent Electron Acceptors with Unparalleled Reduction Potentials

et al. 2023

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A series of fluorinated antimony(V) porphyrins, SbTPP(OMe)2·PF6, SbTPP(OTFE)2·PF6, SbT(4F)PP(OMe)2·PF6, SbT(35F)PP(OMe)2·PF6, SbT(345F)PP(OMe)2·PF6, SbT(4CF3)PP(OMe)2·PF6, SbT(35CF3)PP(OMe)2·PF6, and SbT(35CF3)PP(OTFE)2·PF6, have been synthesized with phenyl [P], 4-fluorophenyl [(4F)P], 3,5-difluorophenyl [(35F)P], 3,4,5-difluorophenyl [(345F)P], 4-trifluoromethylphenyl [(4CF3)P], and 3,5-bis(trifluoromethyl)phenyl [(35CF3)P], in the meso-positions. Additionally, the SbTPP(OTFE)2·PF6 and SbT(35CF3)PP(OTFE)2·PF6 carry trifluoroethoxy units in their axial-positions. The fluorination on the porphyrin peripherals ranges from zero fluorine atoms in SbTPP(OMe)2·PF6 to 30 fluorine atoms in SbT(35CF3)PP(OTFE)2·PF6. X-ray crystallography confirmed the structures of the investigated antimony(V) porphyrins. The absorption spectra depend on the number of fluorine atoms as it is blue-shifted with increasing fluorination. The series also exhibited rich redox chemistry with two reduction processes and one oxidation process. Remarkably, these porphyrins manifested the lowest reduction potentials reported among the main-group porphyrins, which are as low as −0.08 V vs SCE for SbT(35CF3)PP(OTFE)2·PF6. On the contrary, the oxidation potentials were found to be very large, that is equal to 2.20 V vs SCE or even higher for SbT(4CF3)PP(OMe)2·PF6 or SbT(35CF3)PP(OMe)2·PF6 and SbT(35CF3)PP(OTFE)2·PF6, respectively. These unprecedented potentials are due to a combination of two factors: (i) the +5-oxidation state of antimony in the porphyrin cavity and (ii) the presence of the strong electron-withdrawing fluorine atoms on the porphyrin peripherals. Density functional theory (DFT) calculations were used to support the experimental results. The systematic study of antimony(V) porphyrins, especially their high potentials, make them ideal for the construction of photoelectrodes and excellent electron acceptors for photoelectrochemical cells and artificial photosynthetic systems, respectively, for solar energy conversion and storage applications.

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“…A large number of metallophthalocyanine derivatives have so far been studied; however, the metallophthalocyanines with group 15 elements, unlike porphyrins analogues [ 43 , 44 , 45 , 46 , 47 ], were ignored for a long time until the first derivatives of bismuth and antimony were identified [ 48 , 49 , 50 , 51 ], and their structural characterizations are still less explored [ 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 ]. The variable valency of these metals depending on the reaction conditions (III or V) can lead to the formation of various MPc derivatives.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and UV–Vis Characterization of Antimony(III) Phthalocyanine: [(SbPc)2(Sb2I8)(SbBr3)]2

Kubiak

Janczak

2022

Molecules

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A new antimony(III)–phthalocyanine complex with the formula of [(SbPc)2(Sb2I8)(SbBr3)]2 has been obtained in the reaction of pure antimony powder with phthalonitrile under the oxidation conditions by iodine monobromide vapors. The complex crystallizes in the centrosymmetric space group of the triclinic system. Both independent (SbPc)+ units exhibit non-planar conformation, since the Sb(III) is larger than the equilibrium cavity size of the ring and cannot be accommodated without its expansion; thus, the metal protrudes out of the cavity, forming a saucer shape. The centrosymmetric anionic unit of the crystal consists of two (Sb2I8)2− interacted anionic units forming (Sb4I16)4− anionic complex that interacts with two SbBr3 molecules to form [Sb6I16Br6]4− anionic aggregate. Each [Sb6I16Br6]4− anionic aggregate is surrounded by four (SbPc)+ cations forming a supramolecular centrosymmetric (SbPc)4[Sb6I16Br6] complex. Translationally related (SbPc)4[Sb6I16Br6] molecules form a stacking structure along the [100] and [011] directions with N4–N4 distances of 3.55 and 3.53 Å, respectively, between the back-to-back-oriented saucer-shaped (SbPc)+ units. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. The UV–Vis absorption spectra of crystal 1 were taken in CH2Cl2 and toluene solutions in the concentration range from 10−5 to 10−6 mol/L. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ~15 nm in comparison to that in CH2Cl2 solution. Oxidation of (SbPc)4[Sb6I16Br6] yields SbVPc derivative. Both SbIII and SbV phthalocyanine derivatives absorb near infrared light (600–900 nm), which should be intriguing from the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes.

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Synthesis and properties of group 15 element porphyrin peroxides

Abstract: [(Por)M(R)(OORЈ)]

Cited by 17 publications

References 38 publications

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

Fluorinated Antimony(V) Tetraarylporphyrins as High-Valent Electron Acceptors with Unparalleled Reduction Potentials

Synthesis, Structure, and UV–Vis Characterization of Antimony(III) Phthalocyanine: [(SbPc)2(Sb2I8)(SbBr3)]2

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