Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

Daniel Ejarque Granados; Teresa Calvet; Mercè Font-Bardia; Josefina Pons Picart

doi:10.1016/j.molstruc.2022.134896

Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

Daniel Ejarque Granados, Teresa Calvet, Mercè Font-Bardia, Josefina Pons Picart^*

^*Corresponding author for this work

Department of Chemistry

Universitat de Barcelona (UB)

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

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Abstract

The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc) ₂·2H ₂O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4’-bipyridine, 4,4’-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4’-azopyridine, 4,4’-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd ₂(μ-ACA) ₂(ACA) ₂(pyz)(H ₂O) ₂]·2EtOH} _n (1), and double pillars for [Cd ₂(μ-ACA) ₂(ACA) ₂(4,4’-bipy) ₂] _n (2), [Cd ₂(μ-ACA) ₂(ACA) ₂(1,2-bpe) ₂] _n (3) and {[Cd ₂(μ-ACA) ₂(ACA) ₂(4,4’-azpy) ₂]·4,4’-azpy·9H ₂O} _n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4’-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties.

Original language	English
Article number	134896
Number of pages	12
Journal	Journal of Molecular Structure
Volume	1277
DOIs	https://doi.org/10.1016/j.molstruc.2022.134896
Publication status	Published - 5 Apr 2023

Keywords

Cd(II) compounds
Ladder-type coordination polymers
N,N-donor linkers
Photophysical properties
Spacer length effect
X-ray crystal structure

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10.1016/j.molstruc.2022.134896

https://ddd.uab.cat/record/270334

Cite this

@article{6bd69dc065be47a6939679c7236f2af8,

title = "Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers",

abstract = "The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc) 2·2H 2O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4{\textquoteright}-bipyridine, 4,4{\textquoteright}-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4{\textquoteright}-azopyridine, 4,4{\textquoteright}-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd 2(μ-ACA) 2(ACA) 2(pyz)(H 2O) 2]·2EtOH} n (1), and double pillars for [Cd 2(μ-ACA) 2(ACA) 2(4,4{\textquoteright}-bipy) 2] n (2), [Cd 2(μ-ACA) 2(ACA) 2(1,2-bpe) 2] n (3) and {[Cd 2(μ-ACA) 2(ACA) 2(4,4{\textquoteright}-azpy) 2]·4,4{\textquoteright}-azpy·9H 2O} n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4{\textquoteright}-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties.",

keywords = "Cd(II) compounds, Ladder-type coordination polymers, N,N-donor linkers, Photophysical properties, Spacer length effect, X-ray crystal structure",

author = "{Ejarque Granados}, Daniel and Teresa Calvet and Merc{\`e} Font-Bardia and {Pons Picart}, Josefina",

note = "Publisher Copyright: {\textcopyright} 2022 The Author(s)",

year = "2023",

month = apr,

day = "5",

doi = "10.1016/j.molstruc.2022.134896",

language = "English",

volume = "1277",

journal = "Journal of Molecular Structure",

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TY - JOUR

T1 - Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

AU - Ejarque Granados, Daniel

AU - Calvet, Teresa

AU - Font-Bardia, Mercè

AU - Pons Picart, Josefina

PY - 2023/4/5

Y1 - 2023/4/5

N2 - The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc) 2·2H 2O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4’-bipyridine, 4,4’-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4’-azopyridine, 4,4’-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd 2(μ-ACA) 2(ACA) 2(pyz)(H 2O) 2]·2EtOH} n (1), and double pillars for [Cd 2(μ-ACA) 2(ACA) 2(4,4’-bipy) 2] n (2), [Cd 2(μ-ACA) 2(ACA) 2(1,2-bpe) 2] n (3) and {[Cd 2(μ-ACA) 2(ACA) 2(4,4’-azpy) 2]·4,4’-azpy·9H 2O} n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4’-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties.

AB - The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc) 2·2H 2O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4’-bipyridine, 4,4’-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4’-azopyridine, 4,4’-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd 2(μ-ACA) 2(ACA) 2(pyz)(H 2O) 2]·2EtOH} n (1), and double pillars for [Cd 2(μ-ACA) 2(ACA) 2(4,4’-bipy) 2] n (2), [Cd 2(μ-ACA) 2(ACA) 2(1,2-bpe) 2] n (3) and {[Cd 2(μ-ACA) 2(ACA) 2(4,4’-azpy) 2]·4,4’-azpy·9H 2O} n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4’-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties.

KW - Cd(II) compounds

KW - Ladder-type coordination polymers

KW - N,N-donor linkers

KW - Photophysical properties

KW - Spacer length effect

KW - X-ray crystal structure

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U2 - 10.1016/j.molstruc.2022.134896

DO - 10.1016/j.molstruc.2022.134896

M3 - Article

SN - 0022-2860

VL - 1277

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

M1 - 134896

ER -

Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

Abstract

Keywords

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CCDC 2222665: Experimental Crystal Structure Determination

CCDC 2222664: Experimental Crystal Structure Determination

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Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

Abstract

Keywords

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CCDC 2222665: Experimental Crystal Structure Determination

CCDC 2222664: Experimental Crystal Structure Determination

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