Unconventional Pyridyl Ligand Inclusion within a Flexible Metal-Organic Framework Bearing an N,N′-Diethylformamide (DEF)-Solvated Cd5 Cluster Secondary Building Unit

Meng Yao Chao; Jing Chen; Xiao Yu Wu; Rui Yao Wang; Pei Pei Wang; Lifeng Ding; David J. Young; Wen Hua Zhang

doi:10.1002/cplu.202000127

Unconventional Pyridyl Ligand Inclusion within a Flexible Metal-Organic Framework Bearing an N,N′-Diethylformamide (DEF)-Solvated Cd₅ Cluster Secondary Building Unit

Meng Yao Chao, Jing Chen, Xiao Yu Wu, Rui Yao Wang, Pei Pei Wang, Lifeng Ding^*, David J. Young, Wen Hua Zhang

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N,N′-diethylformamide (DEF)-solvated zigzag-shaped Cd₅ cluster secondary building unit (SBU), [Et₂NH₂]₂[Cd₅(BTB)₄(DEF)₂] ⋅ 4.75DEF (1 a, H₃BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl₃ to yield [Et₂NH₂]₂[Cd₅(BTB)₄(DEF)₂] ⋅ xCHCl₃ (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd²⁺ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron-deficient pyridyls preferentially coordinated to the flanking Cd²⁺ of the Cd₅ SBU, as exemplified by [Et₂NH₂]₂[Cd₅(BTB)₄(DEF)₂(PyCHO)₂] ⋅ xSol (2 a, PyCHO=4-pyridinealdehyde) and [Et₂NH₂]₂[Cd₅(BTB)₄(DEF)₂(PyAc)₂] ⋅ xSol (2 b, PyAc=4-acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.

Original language	English
Pages (from-to)	503-509
Number of pages	7
Journal	ChemPlusChem
Volume	85
Issue number	3
DOIs	https://doi.org/10.1002/cplu.202000127
Publication status	Published - 1 Mar 2020

Keywords

cadmium
clusters
flexible metal–organic frameworks
gas uptake
ligand substitution

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10.1002/cplu.202000127

Cite this

@article{ebbefaf59a684264a4a62958f5ff5883,

title = "Unconventional Pyridyl Ligand Inclusion within a Flexible Metal-Organic Framework Bearing an N,N′-Diethylformamide (DEF)-Solvated Cd5 Cluster Secondary Building Unit",

abstract = "A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N,N′-diethylformamide (DEF)-solvated zigzag-shaped Cd5 cluster secondary building unit (SBU), [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ 4.75DEF (1 a, H3BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl3 to yield [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ xCHCl3 (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd2+ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron-deficient pyridyls preferentially coordinated to the flanking Cd2+ of the Cd5 SBU, as exemplified by [Et2NH2]2[Cd5(BTB)4(DEF)2(PyCHO)2] ⋅ xSol (2 a, PyCHO=4-pyridinealdehyde) and [Et2NH2]2[Cd5(BTB)4(DEF)2(PyAc)2] ⋅ xSol (2 b, PyAc=4-acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.",

keywords = "cadmium, clusters, flexible metal–organic frameworks, gas uptake, ligand substitution",

author = "Chao, {Meng Yao} and Jing Chen and Wu, {Xiao Yu} and Wang, {Rui Yao} and Wang, {Pei Pei} and Lifeng Ding and Young, {David J.} and Zhang, {Wen Hua}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = mar,

day = "1",

doi = "10.1002/cplu.202000127",

language = "English",

volume = "85",

pages = "503--509",

journal = "ChemPlusChem",

issn = "2192-6506",

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T1 - Unconventional Pyridyl Ligand Inclusion within a Flexible Metal-Organic Framework Bearing an N,N′-Diethylformamide (DEF)-Solvated Cd5 Cluster Secondary Building Unit

AU - Chao, Meng Yao

AU - Chen, Jing

AU - Wu, Xiao Yu

AU - Wang, Rui Yao

AU - Wang, Pei Pei

AU - Ding, Lifeng

AU - Young, David J.

AU - Zhang, Wen Hua

PY - 2020/3/1

Y1 - 2020/3/1

N2 - A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N,N′-diethylformamide (DEF)-solvated zigzag-shaped Cd5 cluster secondary building unit (SBU), [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ 4.75DEF (1 a, H3BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl3 to yield [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ xCHCl3 (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd2+ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron-deficient pyridyls preferentially coordinated to the flanking Cd2+ of the Cd5 SBU, as exemplified by [Et2NH2]2[Cd5(BTB)4(DEF)2(PyCHO)2] ⋅ xSol (2 a, PyCHO=4-pyridinealdehyde) and [Et2NH2]2[Cd5(BTB)4(DEF)2(PyAc)2] ⋅ xSol (2 b, PyAc=4-acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.

AB - A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N,N′-diethylformamide (DEF)-solvated zigzag-shaped Cd5 cluster secondary building unit (SBU), [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ 4.75DEF (1 a, H3BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl3 to yield [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ xCHCl3 (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd2+ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron-deficient pyridyls preferentially coordinated to the flanking Cd2+ of the Cd5 SBU, as exemplified by [Et2NH2]2[Cd5(BTB)4(DEF)2(PyCHO)2] ⋅ xSol (2 a, PyCHO=4-pyridinealdehyde) and [Et2NH2]2[Cd5(BTB)4(DEF)2(PyAc)2] ⋅ xSol (2 b, PyAc=4-acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.

KW - cadmium

KW - clusters

KW - flexible metal–organic frameworks

KW - gas uptake

KW - ligand substitution

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DO - 10.1002/cplu.202000127

M3 - Article

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