Unveiling Novel Polymorphs of Zirconium-Based Metal-Organic Frameworks from De Novo Syntheses and Phase Transformations

Shengyi Su; Haomiao Xie; Kent O. Kirlikovali; Nathan C. Gianneschi; Omar K. Farha

doi:10.1021/acs.cgd.4c00655

Unveiling Novel Polymorphs of Zirconium-Based Metal-Organic Frameworks from De Novo Syntheses and Phase Transformations

Shengyi Su, Haomiao Xie, Kent O. Kirlikovali, Nathan C. Gianneschi^*, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

Abstract

Polymorphism grants metal-organic frameworks (MOFs) a high degree of structural diversity for various applications. Here, we describe the discovery of three new phases of zirconium-muconate MOFs, denoted as NU-412 (bct), NU-413 (bcu), and NU-414 (reo). NU-412 was first synthesized using formic acid as both modulator and coligand de novo and was crystallographically characterized. The formate coligand in NU-412 could be selectively removed to yield NU-413 with a higher degree of coordinative unsaturation at the Zr₆ node and maintained the channel geometry of the structure. Inspired by the intermediate NU-414 product observed during the growth of NU-412, we investigated the possibility of phase transformations as an approach to yield NU-412 and demonstrated success in accessing novel polymorphs from existing phases.

Original language	English (US)
Pages (from-to)	7025-7030
Number of pages	6
Journal	Crystal Growth and Design
Volume	24
Issue number	17
DOIs	https://doi.org/10.1021/acs.cgd.4c00655
State	Published - Sep 4 2024

ASJC Scopus subject areas

General Chemistry
General Materials Science
Condensed Matter Physics

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title = "Unveiling Novel Polymorphs of Zirconium-Based Metal-Organic Frameworks from De Novo Syntheses and Phase Transformations",

abstract = "Polymorphism grants metal-organic frameworks (MOFs) a high degree of structural diversity for various applications. Here, we describe the discovery of three new phases of zirconium-muconate MOFs, denoted as NU-412 (bct), NU-413 (bcu), and NU-414 (reo). NU-412 was first synthesized using formic acid as both modulator and coligand de novo and was crystallographically characterized. The formate coligand in NU-412 could be selectively removed to yield NU-413 with a higher degree of coordinative unsaturation at the Zr6 node and maintained the channel geometry of the structure. Inspired by the intermediate NU-414 product observed during the growth of NU-412, we investigated the possibility of phase transformations as an approach to yield NU-412 and demonstrated success in accessing novel polymorphs from existing phases.",

author = "Shengyi Su and Haomiao Xie and Kirlikovali, {Kent O.} and Gianneschi, {Nathan C.} and Farha, {Omar K.}",

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AU - Su, Shengyi

AU - Xie, Haomiao

AU - Kirlikovali, Kent O.

AU - Gianneschi, Nathan C.

AU - Farha, Omar K.

PY - 2024/9/4

Y1 - 2024/9/4

N2 - Polymorphism grants metal-organic frameworks (MOFs) a high degree of structural diversity for various applications. Here, we describe the discovery of three new phases of zirconium-muconate MOFs, denoted as NU-412 (bct), NU-413 (bcu), and NU-414 (reo). NU-412 was first synthesized using formic acid as both modulator and coligand de novo and was crystallographically characterized. The formate coligand in NU-412 could be selectively removed to yield NU-413 with a higher degree of coordinative unsaturation at the Zr6 node and maintained the channel geometry of the structure. Inspired by the intermediate NU-414 product observed during the growth of NU-412, we investigated the possibility of phase transformations as an approach to yield NU-412 and demonstrated success in accessing novel polymorphs from existing phases.

AB - Polymorphism grants metal-organic frameworks (MOFs) a high degree of structural diversity for various applications. Here, we describe the discovery of three new phases of zirconium-muconate MOFs, denoted as NU-412 (bct), NU-413 (bcu), and NU-414 (reo). NU-412 was first synthesized using formic acid as both modulator and coligand de novo and was crystallographically characterized. The formate coligand in NU-412 could be selectively removed to yield NU-413 with a higher degree of coordinative unsaturation at the Zr6 node and maintained the channel geometry of the structure. Inspired by the intermediate NU-414 product observed during the growth of NU-412, we investigated the possibility of phase transformations as an approach to yield NU-412 and demonstrated success in accessing novel polymorphs from existing phases.

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Unveiling Novel Polymorphs of Zirconium-Based Metal-Organic Frameworks from De Novo Syntheses and Phase Transformations

Abstract

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