A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis

Susanne Reischauer; Courtney S. Smoljan; Jabor Rabeah; Haomiao Xie; Filip Formalik; Zhihengyu Chen; Simon M. Vornholt; Fanrui Sha; Karena W. Chapman; Randall Q. Snurr; Justin M. Notestein; Omar K. Farha

doi:10.1021/acsami.4c03651

A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis

Susanne Reischauer, Courtney S. Smoljan, Jabor Rabeah, Haomiao Xie, Filip Formalik, Zhihengyu Chen, Simon M. Vornholt, Fanrui Sha, Karena W. Chapman, Randall Q. Snurr, Justin M. Notestein^*, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Metal-organic frameworks (MOFs) have garnered substantial attention for their unique properties, such as high porosity and tunable structures, making them versatile for various applications. This paper constructs photoactive titanium-organic frameworks by combining Ti(IV) clusters and a bipyridine linker. The MOF is synthesized in situ through imine condensation, resulting in NU-2300. Subsequent ex situ nickel salt complexation results in NU-2300-Ni, which is then used for light-mediated carbon-heteroatom cross-couplings. The photophysical properties of the metallaphotocatalyst were investigated by UV-vis and EPR analyses, and both the Ti cluster and the bipyridine linker were found to contribute to successful catalysis, making it a tandem catalyst. The heterogeneous material retained its performance through five cycles of thioetherification. This work contributes not only to MOF synthetic strategies but also to expanding MOF applications as recyclable, tandem metallaphotocatalysts.

Original language	English (US)
Pages (from-to)	33371-33378
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	16
Issue number	26
DOIs	https://doi.org/10.1021/acsami.4c03651
State	Published - Jul 3 2024

Keywords

cross-coupling reaction
metallaphotocatalysts
nickel catalysis
photocatalyst
titanium−organic framework

ASJC Scopus subject areas

General Materials Science

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title = "A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis",

abstract = "Metal-organic frameworks (MOFs) have garnered substantial attention for their unique properties, such as high porosity and tunable structures, making them versatile for various applications. This paper constructs photoactive titanium-organic frameworks by combining Ti(IV) clusters and a bipyridine linker. The MOF is synthesized in situ through imine condensation, resulting in NU-2300. Subsequent ex situ nickel salt complexation results in NU-2300-Ni, which is then used for light-mediated carbon-heteroatom cross-couplings. The photophysical properties of the metallaphotocatalyst were investigated by UV-vis and EPR analyses, and both the Ti cluster and the bipyridine linker were found to contribute to successful catalysis, making it a tandem catalyst. The heterogeneous material retained its performance through five cycles of thioetherification. This work contributes not only to MOF synthetic strategies but also to expanding MOF applications as recyclable, tandem metallaphotocatalysts.",

keywords = "cross-coupling reaction, metallaphotocatalysts, nickel catalysis, photocatalyst, titanium−organic framework",

author = "Susanne Reischauer and Smoljan, {Courtney S.} and Jabor Rabeah and Haomiao Xie and Filip Formalik and Zhihengyu Chen and Vornholt, {Simon M.} and Fanrui Sha and Chapman, {Karena W.} and Snurr, {Randall Q.} and Notestein, {Justin M.} and Farha, {Omar K.}",

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year = "2024",

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doi = "10.1021/acsami.4c03651",

language = "English (US)",

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T1 - A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis

AU - Reischauer, Susanne

AU - Smoljan, Courtney S.

AU - Rabeah, Jabor

AU - Xie, Haomiao

AU - Formalik, Filip

AU - Chen, Zhihengyu

AU - Vornholt, Simon M.

AU - Sha, Fanrui

AU - Chapman, Karena W.

AU - Snurr, Randall Q.

AU - Notestein, Justin M.

AU - Farha, Omar K.

PY - 2024/7/3

Y1 - 2024/7/3

N2 - Metal-organic frameworks (MOFs) have garnered substantial attention for their unique properties, such as high porosity and tunable structures, making them versatile for various applications. This paper constructs photoactive titanium-organic frameworks by combining Ti(IV) clusters and a bipyridine linker. The MOF is synthesized in situ through imine condensation, resulting in NU-2300. Subsequent ex situ nickel salt complexation results in NU-2300-Ni, which is then used for light-mediated carbon-heteroatom cross-couplings. The photophysical properties of the metallaphotocatalyst were investigated by UV-vis and EPR analyses, and both the Ti cluster and the bipyridine linker were found to contribute to successful catalysis, making it a tandem catalyst. The heterogeneous material retained its performance through five cycles of thioetherification. This work contributes not only to MOF synthetic strategies but also to expanding MOF applications as recyclable, tandem metallaphotocatalysts.

AB - Metal-organic frameworks (MOFs) have garnered substantial attention for their unique properties, such as high porosity and tunable structures, making them versatile for various applications. This paper constructs photoactive titanium-organic frameworks by combining Ti(IV) clusters and a bipyridine linker. The MOF is synthesized in situ through imine condensation, resulting in NU-2300. Subsequent ex situ nickel salt complexation results in NU-2300-Ni, which is then used for light-mediated carbon-heteroatom cross-couplings. The photophysical properties of the metallaphotocatalyst were investigated by UV-vis and EPR analyses, and both the Ti cluster and the bipyridine linker were found to contribute to successful catalysis, making it a tandem catalyst. The heterogeneous material retained its performance through five cycles of thioetherification. This work contributes not only to MOF synthetic strategies but also to expanding MOF applications as recyclable, tandem metallaphotocatalysts.

KW - cross-coupling reaction

KW - metallaphotocatalysts

KW - nickel catalysis

KW - photocatalyst

KW - titanium−organic framework

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A Titanium-Based Metal-Organic Framework For Tandem Metallaphotocatalysis

Abstract

Keywords

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