Antimony(+5) ion induced tunable intramolecular charge transfer in hypervalent antimony(<scp>v</scp>) porphyrins

Holzer, Noah; Sharma, J.; Peterson, Steven A.; Bayard, Brandon J.; Нестеров, В. Н.; Karr, Paul A.; D’Souza, Francis; Poddutoori, Prashanth K.

doi:10.1039/d2dt00675h

Cited by 9 publications

(57 citation statements)

References 45 publications

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“…Variations in the reaction times and purification method were used depending on the specific porphyrin. As previously observed with the antimony(V) porphyrins, 36 the time required for the reaction between axial P−Cl bonds and methanol (i.e., P−Cl to P−OMe) strongly depends on the position and number of the methoxy substitutions. The trend observed in the reaction times for complete axial ligand substitution of the dichlorophosphorus-(V) porphyrins with methanol is as follows:…”

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinssupporting

confidence: 57%

“…The absorption spectra of H 2 P, H 2 MP, H 2 DMP, and H 2 345TMP are reported elsewhere. 36 The absorption spectra of H 2 246TMP are shown in Figure S11. Based on the absorption data, it is evident that the electronic structure of the free-base porphyrins is very similar in all five compounds.…”

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

“…The cyclic and differential voltammograms of H 2 246TMP are shown in Figure S14a, and the rest of the free-base porphyrin (H 2 P, H 2 MP, H 2 DMP, H 2 345TMP) data were reported elsewhere. 36 However, for comparison purposes all of the free-base porphyrin redox data are summarized in Table S12. The data indicate that the H 2 246TMP is richer in electron density, as it is relatively easy to oxidize and difficult to reduce than the rest of the porphyrins.…”

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

“…The trend in the reactivity toward nucleophilic substitution is identical to the trend observed with the antimony(V) porphyrins. 36 However, the phosphorus series is much more reactive than the antimony series, with reaction times for some of the corresponding porphyrins being an order of magnitude smaller.…”

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

“…The photophysical and redox properties were established using a wide variety of analytical and spectroscopic methods as well as computational methods. Finally, the present phosphorus(V) porphyrin series is compared to their recently reported antimony(V) porphyrin counterparts. The present work uncovers the meso -aryl group-induced photophysical properties of the phosphorus(V) porphyrin.…”

Section: Introductionmentioning

confidence: 99%

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Hypervalent Phosphorus(V) Porphyrins with meso-Methoxyphenyl Substituents: Significance of the Number and Position of Methoxy Groups in Promoting Intramolecular Charge Transfer

et al. 2022

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To study the photophysical and redox properties as a function of meso-aryl units, a series of hypervalent phosphorus(V) porphyrins, PP(OMe)2·PF6, PMP(OMe)2·PF6, PDMP(OMe)2·PF6, P345TMP(OMe)2·PF6, and P246TMP(OMe)2·PF6, with phenyl (P), 4-methoxyphenyl (MP), 3,5-dimethoxyphenyl (DMP), 3,4,5-trimethoxyphenyl (345TMP), and 2,4,6-trimethoxyphenyl (246TMP) units, respectively, have been synthesized. The P(+5) in the cavity makes the porphyrin ring electron-poor, whereas the methoxy groups make the meso-phenyl rings electron-rich. The presence of electron-rich and electron-poor portions within the porphyrin molecule promoted an intramolecular charge transfer (ICT). Also, the study suggests that the ICT depends on the number and position of the methoxy groups. The ICT is more prominent in m-methoxy-substituted phosphorus(V) porphyrins (PDMP(OMe)2.PF6, P345TMP(OMe)2·PF6) and almost no ICT was found in no-methoxy, o-methoxy, and/or p-methoxy phosphorus(V) porphyrins (PP(OMe)2·PF6, PMP(OMe)2·PF6, P246TMP(OMe)2·PF6). Transient absorption studies indicate that the ICT takes place on the picosecond time scale. The most striking results come from P246TMP(OMe)2·PF6, where each phenyl ring carries three methoxy units, like the P345TMP(OMe)2·PF6, but it failed to induce the ICT process. Electrochemical studies and time-dependent density functional theory (TD-DFT) calculations were used to support the experimental results. This study extensively explores why and how slight variations in meso-aryl substitutions lead to intricate changes in the photophysical and redox properties of phosphorus(V) porphyrins.

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Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinssupporting

confidence: 57%

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

Section: Synthesis Of Axial Dimethoxyphosphorus(v) Porphyrinsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hypervalent Phosphorus(V) Porphyrins with meso-Methoxyphenyl Substituents: Significance of the Number and Position of Methoxy Groups in Promoting Intramolecular Charge Transfer

et al. 2022

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Main-group porphyrins in artificial photosynthesis

Poddutoori

2023

Photosynthesis

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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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Antimony(+5) ion induced tunable intramolecular charge transfer in hypervalent antimony(v) porphyrins

Abstract: Antimony(+5) insertion induces both electron-rich and electron-poor parts within the porphyrin structure resulting in a push–pull style intramolecular charge transfer.

Cited by 9 publications

References 45 publications

Hypervalent Phosphorus(V) Porphyrins with meso-Methoxyphenyl Substituents: Significance of the Number and Position of Methoxy Groups in Promoting Intramolecular Charge Transfer

Hypervalent Phosphorus(V) Porphyrins with meso-Methoxyphenyl Substituents: Significance of the Number and Position of Methoxy Groups in Promoting Intramolecular Charge Transfer

Main-group porphyrins in artificial photosynthesis

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

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