P -Xylylenediamine derived ligands as flexible connectors in the design of porous coordination polymers

Adrian J. Emerson; Gregory P. Knowles; Alan L. Chaffee; Stuart R. Batten; David R. Turner

doi:10.1039/c9ce00371a

P -Xylylenediamine derived ligands as flexible connectors in the design of porous coordination polymers

Adrian J. Emerson, Gregory P. Knowles, Alan L. Chaffee, Stuart R. Batten, David R. Turner

School of Chemistry

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

Abstract

The use of flexible ligands in coordination polymers provides both opportunities and unpredictability. A new series of flexible ligands derived from p-xylylenediamine, which vary in the positioning of carboxylic acid functional groups, have been found to form a series of coordination polymers and a discrete coordination complex. Use of the tetra-substituted meta-carboxylic acid ligand N,N,N′,N′-tetra(3-carboxybenzyl)-p-xylylenediamine, isolated as its dihydrochloride salt (H ₆ M ₄ pxy)Cl ₂ , resulted in the simultaneous formation of two products from the same synthetic conditions. One of these products was a discrete cage-type coordination complex of the form [Cu ₄ (M ₄ pxy) ₂ (DMF) ₂ (OH ₂ )] (1), while the other product was the two-dimensional coordination polymer poly-[Cu ₂ (M ₄ pxy)(OH ₂ ) ₂ ] (2). Synthesis utilising the tetra-substituted para-carboxylic acid ligand, isolated as N,N,N′,N′-tetra(4-carboxybenzyl)-p-xylylenediamine dihydrochloride (H ₆ P ₄ pxy)Cl ₂ , resulted in the formation of multiple two-dimensional coordination polymers, poly-[Cu ₂ (P ₄ pxy)(DMF)(OH ₂ )]·2DMF·3H ₂ O (3·2DMF·3H ₂ O), poly-[Mn ₂ (P ₄ pxy)(DMA) ₂ ] (4), poly-[Co ₄ (P ₄ pxy) ₂ (DMF) ₂ (μ-OH ₂ ) ₂ (OH ₂ ) ₂ ]·6DMF·4H ₂ O (5·6DMF·4H ₂ O) and poly-[Cd ₂ (P ₄ pxy)(OH ₂ ) ₂ ]·DMA·3H ₂ O (6·DMA·3H ₂ O). The last of these materials, a three-dimensional coordination polymer, was found to adsorb approximately 32 cm ³ g ^-1 STP of CO ₂ at atmospheric pressure at 273 K.

Original language	English
Pages (from-to)	3074-3085
Number of pages	12
Journal	CrystEngComm
Volume	21
Issue number	19
DOIs	https://doi.org/10.1039/c9ce00371a
Publication status	Published - 1 Jan 2019

Keywords

Chelation
Ligands
Atmospheric pressure
Carboxylic acids

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10.1039/c9ce00371a

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Cite this

@article{8ed0078d385842aebbd094632eeec9f2,

title = "P -Xylylenediamine derived ligands as flexible connectors in the design of porous coordination polymers",

abstract = " The use of flexible ligands in coordination polymers provides both opportunities and unpredictability. A new series of flexible ligands derived from p-xylylenediamine, which vary in the positioning of carboxylic acid functional groups, have been found to form a series of coordination polymers and a discrete coordination complex. Use of the tetra-substituted meta-carboxylic acid ligand N,N,N′,N′-tetra(3-carboxybenzyl)-p-xylylenediamine, isolated as its dihydrochloride salt (H 6 M 4 pxy)Cl 2 , resulted in the simultaneous formation of two products from the same synthetic conditions. One of these products was a discrete cage-type coordination complex of the form [Cu 4 (M 4 pxy) 2 (DMF) 2 (OH 2 )] (1), while the other product was the two-dimensional coordination polymer poly-[Cu 2 (M 4 pxy)(OH 2 ) 2 ] (2). Synthesis utilising the tetra-substituted para-carboxylic acid ligand, isolated as N,N,N′,N′-tetra(4-carboxybenzyl)-p-xylylenediamine dihydrochloride (H 6 P 4 pxy)Cl 2 , resulted in the formation of multiple two-dimensional coordination polymers, poly-[Cu 2 (P 4 pxy)(DMF)(OH 2 )]·2DMF·3H 2 O (3·2DMF·3H 2 O), poly-[Mn 2 (P 4 pxy)(DMA) 2 ] (4), poly-[Co 4 (P 4 pxy) 2 (DMF) 2 (μ-OH 2 ) 2 (OH 2 ) 2 ]·6DMF·4H 2 O (5·6DMF·4H 2 O) and poly-[Cd 2 (P 4 pxy)(OH 2 ) 2 ]·DMA·3H 2 O (6·DMA·3H 2 O). The last of these materials, a three-dimensional coordination polymer, was found to adsorb approximately 32 cm 3 g -1 STP of CO 2 at atmospheric pressure at 273 K. ",

keywords = "Chelation, Ligands, Atmospheric pressure, Carboxylic acids",

author = "Emerson, {Adrian J.} and Knowles, {Gregory P.} and Chaffee, {Alan L.} and Batten, {Stuart R.} and Turner, {David R.}",

year = "2019",

month = jan,

day = "1",

doi = "10.1039/c9ce00371a",

language = "English",

volume = "21",

pages = "3074--3085",

journal = "CrystEngComm",

issn = "1466-8033",

publisher = "The Royal Society of Chemistry",

number = "19",

}

TY - JOUR

T1 - P -Xylylenediamine derived ligands as flexible connectors in the design of porous coordination polymers

AU - Emerson, Adrian J.

AU - Knowles, Gregory P.

AU - Chaffee, Alan L.

AU - Batten, Stuart R.

AU - Turner, David R.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 6 M 4 pxy)Cl 2 4 (M 4 pxy) 2 (DMF) 2 (OH 2 2 (M 4 pxy)(OH 2 ) 2 6 P 4 pxy)Cl 2 2 (P 4 pxy)(DMF)(OH 2 )]·2DMF·3H 2 O (3·2DMF·3H 2 O), poly-[Mn 2 (P 4 pxy)(DMA) 2 ] (4), poly-[Co 4 (P 4 pxy) 2 (DMF) 2 (μ-OH 2 ) 2 (OH 2 ) 2 ]·6DMF·4H 2 O (5·6DMF·4H 2 O) and poly-[Cd 2 (P 4 pxy)(OH 2 ) 2 ]·DMA·3H 2 O (6·DMA·3H 2 3 g -1 STP of CO 2 The use of flexible ligands in coordination polymers provides both opportunities and unpredictability. A new series of flexible ligands derived from p-xylylenediamine, which vary in the positioning of carboxylic acid functional groups, have been found to form a series of coordination polymers and a discrete coordination complex. Use of the tetra-substituted meta-carboxylic acid ligand N,N,N′,N′-tetra(3-carboxybenzyl)-p-xylylenediamine, isolated as its dihydrochloride salt (H , resulted in the simultaneous formation of two products from the same synthetic conditions. One of these products was a discrete cage-type coordination complex of the form [Cu )] (1), while the other product was the two-dimensional coordination polymer poly-[Cu ] (2). Synthesis utilising the tetra-substituted para-carboxylic acid ligand, isolated as N,N,N′,N′-tetra(4-carboxybenzyl)-p-xylylenediamine dihydrochloride (H , resulted in the formation of multiple two-dimensional coordination polymers, poly-[Cu O). The last of these materials, a three-dimensional coordination polymer, was found to adsorb approximately 32 cm at atmospheric pressure at 273 K.

AB - The use of flexible ligands in coordination polymers provides both opportunities and unpredictability. A new series of flexible ligands derived from p-xylylenediamine, which vary in the positioning of carboxylic acid functional groups, have been found to form a series of coordination polymers and a discrete coordination complex. Use of the tetra-substituted meta-carboxylic acid ligand N,N,N′,N′-tetra(3-carboxybenzyl)-p-xylylenediamine, isolated as its dihydrochloride salt (H 6 M 4 pxy)Cl 2 , resulted in the simultaneous formation of two products from the same synthetic conditions. One of these products was a discrete cage-type coordination complex of the form [Cu 4 (M 4 pxy) 2 (DMF) 2 (OH 2 )] (1), while the other product was the two-dimensional coordination polymer poly-[Cu 2 (M 4 pxy)(OH 2 ) 2 ] (2). Synthesis utilising the tetra-substituted para-carboxylic acid ligand, isolated as N,N,N′,N′-tetra(4-carboxybenzyl)-p-xylylenediamine dihydrochloride (H 6 P 4 pxy)Cl 2 , resulted in the formation of multiple two-dimensional coordination polymers, poly-[Cu 2 (P 4 pxy)(DMF)(OH 2 )]·2DMF·3H 2 O (3·2DMF·3H 2 O), poly-[Mn 2 (P 4 pxy)(DMA) 2 ] (4), poly-[Co 4 (P 4 pxy) 2 (DMF) 2 (μ-OH 2 ) 2 (OH 2 ) 2 ]·6DMF·4H 2 O (5·6DMF·4H 2 O) and poly-[Cd 2 (P 4 pxy)(OH 2 ) 2 ]·DMA·3H 2 O (6·DMA·3H 2 O). The last of these materials, a three-dimensional coordination polymer, was found to adsorb approximately 32 cm 3 g -1 STP of CO 2 at atmospheric pressure at 273 K.

KW - Chelation

KW - Ligands

KW - Atmospheric pressure

KW - Carboxylic acids

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U2 - 10.1039/c9ce00371a

DO - 10.1039/c9ce00371a

M3 - Article

AN - SCOPUS:85065830302

VL - 21

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JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 19

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