Hierarchical Hybrid Metal-Organic Frameworks

Tuning the Visible/Near-Infrared Optical Properties by a Combination of Porphyrin and Its Isomer Units

Yufeng Yang, Masatoshi Ishida, Yuhsuke Yasutake, Susumu Fukatsu, Chihoko Fukakusa, Masa-Aki Morikawa, Teppei Yamada, Nobuo Kimizuka, Hiroyuki Furuta

Research output: Contribution to journalArticle

Abstract

Hybrid metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and photosensitization capabilities. The Förster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed porphyrin "substitute" into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.

Original languageEnglish
Pages (from-to)4647-4656
Number of pages10
JournalInorganic Chemistry
Volume58
Issue number7
DOIs
Publication statusPublished - Apr 1 2019

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Porphyrins
porphyrins
Isomers
isomers
Optical properties
Tuning
Metals
tuning
Infrared radiation
optical properties
metals
Shells (structures)
Scanning
Singlet Oxygen
scanning
Photoexcitation
Infrared absorption
pigments
photoexcitation
Excited states

Cite this

@article{17095bea2f19456dafb85fa2838ee697,
title = "Hierarchical Hybrid Metal-Organic Frameworks: Tuning the Visible/Near-Infrared Optical Properties by a Combination of Porphyrin and Its Isomer Units",
abstract = "Hybrid metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and photosensitization capabilities. The F{\"o}rster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed porphyrin {"}substitute{"} into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.",
author = "Yufeng Yang and Masatoshi Ishida and Yuhsuke Yasutake and Susumu Fukatsu and Chihoko Fukakusa and Masa-Aki Morikawa and Teppei Yamada and Nobuo Kimizuka and Hiroyuki Furuta",
year = "2019",
month = "4",
day = "1",
doi = "10.1021/acs.inorgchem.9b00251",
language = "English",
volume = "58",
pages = "4647--4656",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "7",

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TY - JOUR

T1 - Hierarchical Hybrid Metal-Organic Frameworks

T2 - Tuning the Visible/Near-Infrared Optical Properties by a Combination of Porphyrin and Its Isomer Units

AU - Yang, Yufeng

AU - Ishida, Masatoshi

AU - Yasutake, Yuhsuke

AU - Fukatsu, Susumu

AU - Fukakusa, Chihoko

AU - Morikawa, Masa-Aki

AU - Yamada, Teppei

AU - Kimizuka, Nobuo

AU - Furuta, Hiroyuki

PY - 2019/4/1

Y1 - 2019/4/1

N2 - Hybrid metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and photosensitization capabilities. The Förster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed porphyrin "substitute" into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.

AB - Hybrid metal-organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and photosensitization capabilities. The Förster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed porphyrin "substitute" into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.

U2 - 10.1021/acs.inorgchem.9b00251

DO - 10.1021/acs.inorgchem.9b00251

M3 - Article

VL - 58

SP - 4647

EP - 4656

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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