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

Noah Holzer; Jatan K. Sharma; Steven Peterson; Brandon J. Bayard; Vladimir N. Nesterov; Paul A. Karr; Francis D'Souza; Prashanth K. Poddutoori

doi:10.1039/d2dt00675h

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

Noah Holzer, Jatan K. Sharma, Steven Peterson, Brandon J. Bayard, Vladimir N. Nesterov, Paul A. Karr, Francis D'Souza, Prashanth K. Poddutoori

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Abstract

The +5 oxidation state of antimony induced push-pull style intramolecular charge transfer in an elegantly designed axial dimethoxyantimony(v) porphyrin series: SbP(OMe)₂·PF₆, SbMP(OMe)₂·PF₆, SbDMP(OMe)₂·PF₆, SbTMP(OMe)₂·PF₆ with phenyl (P), 4-methoxyphenyl (MP), 3,5-dimethoxyphenyl (DMP), and 3,4,5-trimethoxyphenyl (TMP) units, respectively, in its meso positions. The Sb(+5) made the porphyrin ring electron-poor, whereas the methoxy groups on the phenyl unit produced electron-rich sites within the molecule. The presence of electron-poor and electron-rich parts in the same molecule resulted in a push-pull type intramolecular charge transfer (ICT). However, the ICT is strongly dependent on the position of the methoxy groups on the phenyl ring. The charge transfer character is more pronounced in meta-methoxy substituted antimony(v) derivatives (SbDMP(OMe)₂·PF₆, SbTMP(OMe)₂·PF₆) than the para-methoxy or no-methoxy substituted antimony(v) derivatives (SbP(OMe)₂·PF₆, SbMP(OMe)₂·PF₆). Steady-state and transient spectroscopic techniques, as well as solvatochromism techniques, were employed to establish the tunable ICT. Additionally, time-dependant density functional theory (TD-DFT) calculations were used to complement the experimental results. The systematic study of antimony(v) porphyrins, especially the tunable push-pull nature could play an important role in instigating high yield charge-separated states in multi-modular donor-acceptor systems for solar energy conversion and molecular electronic and photonic applications.

Original language	English (US)
Pages (from-to)	5890-5903
Number of pages	14
Journal	Dalton Transactions
Volume	51
Issue number	15
DOIs	https://doi.org/10.1039/d2dt00675h
State	Published - Mar 21 2022

Bibliographical note

Funding Information:
This work was supported by the University of Minnesota - Grant-in-Aid program (No. 380228) and the University of Minnesota Duluth - Advanced Materials Center - SEED Grant program to PPK and by the National Science Foundation (2000988) to FD. The authors also acknowledge NSF-MRI Program (CHE-1726652), and the University of North Texas for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. The computational work was completed at the Holland Computing Center of the University of Nebraska, which receives support from the Nebraska Research Initiative.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

Keywords

Antimony
Density Functional Theory
Electrons
Porphyrins/chemistry
Solar Energy

PubMed: MeSH publication types

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

abstract = "The +5 oxidation state of antimony induced push-pull style intramolecular charge transfer in an elegantly designed axial dimethoxyantimony(v) porphyrin series: SbP(OMe)2·PF6, SbMP(OMe)2·PF6, SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6 with phenyl (P), 4-methoxyphenyl (MP), 3,5-dimethoxyphenyl (DMP), and 3,4,5-trimethoxyphenyl (TMP) units, respectively, in its meso positions. The Sb(+5) made the porphyrin ring electron-poor, whereas the methoxy groups on the phenyl unit produced electron-rich sites within the molecule. The presence of electron-poor and electron-rich parts in the same molecule resulted in a push-pull type intramolecular charge transfer (ICT). However, the ICT is strongly dependent on the position of the methoxy groups on the phenyl ring. The charge transfer character is more pronounced in meta-methoxy substituted antimony(v) derivatives (SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6) than the para-methoxy or no-methoxy substituted antimony(v) derivatives (SbP(OMe)2·PF6, SbMP(OMe)2·PF6). Steady-state and transient spectroscopic techniques, as well as solvatochromism techniques, were employed to establish the tunable ICT. Additionally, time-dependant density functional theory (TD-DFT) calculations were used to complement the experimental results. The systematic study of antimony(v) porphyrins, especially the tunable push-pull nature could play an important role in instigating high yield charge-separated states in multi-modular donor-acceptor systems for solar energy conversion and molecular electronic and photonic applications.",

keywords = "Antimony, Density Functional Theory, Electrons, Porphyrins/chemistry, Solar Energy",

author = "Noah Holzer and Sharma, {Jatan K.} and Steven Peterson and Bayard, {Brandon J.} and Nesterov, {Vladimir N.} and Karr, {Paul A.} and Francis D'Souza and Poddutoori, {Prashanth K.}",

note = "Funding Information: This work was supported by the University of Minnesota - Grant-in-Aid program (No. 380228) and the University of Minnesota Duluth - Advanced Materials Center - SEED Grant program to PPK and by the National Science Foundation (2000988) to FD. The authors also acknowledge NSF-MRI Program (CHE-1726652), and the University of North Texas for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. The computational work was completed at the Holland Computing Center of the University of Nebraska, which receives support from the Nebraska Research Initiative. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

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doi = "10.1039/d2dt00675h",

language = "English (US)",

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T1 - Antimony(+5) ion induced tunable intramolecular charge transfer in hypervalent antimony(v) porphyrins

AU - Holzer, Noah

AU - Sharma, Jatan K.

AU - Peterson, Steven

AU - Bayard, Brandon J.

AU - Nesterov, Vladimir N.

AU - Karr, Paul A.

AU - D'Souza, Francis

AU - Poddutoori, Prashanth K.

N1 - Funding Information: This work was supported by the University of Minnesota - Grant-in-Aid program (No. 380228) and the University of Minnesota Duluth - Advanced Materials Center - SEED Grant program to PPK and by the National Science Foundation (2000988) to FD. The authors also acknowledge NSF-MRI Program (CHE-1726652), and the University of North Texas for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. The computational work was completed at the Holland Computing Center of the University of Nebraska, which receives support from the Nebraska Research Initiative. Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/3/21

Y1 - 2022/3/21

N2 - The +5 oxidation state of antimony induced push-pull style intramolecular charge transfer in an elegantly designed axial dimethoxyantimony(v) porphyrin series: SbP(OMe)2·PF6, SbMP(OMe)2·PF6, SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6 with phenyl (P), 4-methoxyphenyl (MP), 3,5-dimethoxyphenyl (DMP), and 3,4,5-trimethoxyphenyl (TMP) units, respectively, in its meso positions. The Sb(+5) made the porphyrin ring electron-poor, whereas the methoxy groups on the phenyl unit produced electron-rich sites within the molecule. The presence of electron-poor and electron-rich parts in the same molecule resulted in a push-pull type intramolecular charge transfer (ICT). However, the ICT is strongly dependent on the position of the methoxy groups on the phenyl ring. The charge transfer character is more pronounced in meta-methoxy substituted antimony(v) derivatives (SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6) than the para-methoxy or no-methoxy substituted antimony(v) derivatives (SbP(OMe)2·PF6, SbMP(OMe)2·PF6). Steady-state and transient spectroscopic techniques, as well as solvatochromism techniques, were employed to establish the tunable ICT. Additionally, time-dependant density functional theory (TD-DFT) calculations were used to complement the experimental results. The systematic study of antimony(v) porphyrins, especially the tunable push-pull nature could play an important role in instigating high yield charge-separated states in multi-modular donor-acceptor systems for solar energy conversion and molecular electronic and photonic applications.

AB - The +5 oxidation state of antimony induced push-pull style intramolecular charge transfer in an elegantly designed axial dimethoxyantimony(v) porphyrin series: SbP(OMe)2·PF6, SbMP(OMe)2·PF6, SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6 with phenyl (P), 4-methoxyphenyl (MP), 3,5-dimethoxyphenyl (DMP), and 3,4,5-trimethoxyphenyl (TMP) units, respectively, in its meso positions. The Sb(+5) made the porphyrin ring electron-poor, whereas the methoxy groups on the phenyl unit produced electron-rich sites within the molecule. The presence of electron-poor and electron-rich parts in the same molecule resulted in a push-pull type intramolecular charge transfer (ICT). However, the ICT is strongly dependent on the position of the methoxy groups on the phenyl ring. The charge transfer character is more pronounced in meta-methoxy substituted antimony(v) derivatives (SbDMP(OMe)2·PF6, SbTMP(OMe)2·PF6) than the para-methoxy or no-methoxy substituted antimony(v) derivatives (SbP(OMe)2·PF6, SbMP(OMe)2·PF6). Steady-state and transient spectroscopic techniques, as well as solvatochromism techniques, were employed to establish the tunable ICT. Additionally, time-dependant density functional theory (TD-DFT) calculations were used to complement the experimental results. The systematic study of antimony(v) porphyrins, especially the tunable push-pull nature could play an important role in instigating high yield charge-separated states in multi-modular donor-acceptor systems for solar energy conversion and molecular electronic and photonic applications.

KW - Antimony

KW - Density Functional Theory

KW - Electrons

KW - Porphyrins/chemistry

KW - Solar Energy

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U2 - 10.1039/d2dt00675h

DO - 10.1039/d2dt00675h

M3 - Article

C2 - 35348158

AN - SCOPUS:85128398344

SN - 1477-9226

VL - 51

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EP - 5903

JO - Dalton Transactions

JF - Dalton Transactions

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ER -

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

Abstract

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Keywords

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