Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile doub...

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Main Authors:	Santokh S. Tandon, Scott D. Bunge, Neil Patel, Esther C. Wang, Laurence K. Thompson
Format:	Article
Language:	English
Published:	MDPI AG 2020-11-01
Series:	Molecules
Subjects:	self-assembly of supramolecular architectures antiferromagnetically-coupled copper(II) complexes magneto-structural correlations phenolate and azido bridged copper(II) complexes
Online Access:	https://www.mdpi.com/1420-3049/25/23/5549

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spelling	doaj-d17547fa5f624e9a9b4fc6a9cd232fd52020-11-27T08:11:34ZengMDPI AGMolecules1420-30492020-11-01255549554910.3390/molecules25235549Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural ComplexitiesSantokh S. Tandon0Scott D. Bunge1Neil Patel2Esther C. Wang3Laurence K. Thompson4Department of Chemistry and Biochemistry, Kent State University-Salem Campus, Salem, OH 44460, USADepartment of Chemistry and Biochemistry, Kent State University, Kent, OH 44242, USADepartment of Chemistry and Biochemistry, Kent State University, Kent, OH 44242, USADepartment of Chemistry and Biochemistry, Kent State University, Kent, OH 44242, USADepartment of Chemistry, Memorial University, St. John’s Newfoundland, NL A1B 3X7, CanadaThe self-assembly of 2,6-diformyl-4-methylphenol (<b>DFMP</b>) and 1-amino-2-propanol (<b>AP</b>)/2-amino-1,3-propanediol (<b>APD</b>) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H<sub>3</sub>L and H<sub>5</sub>L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu<sub>4</sub>(HL<sup>2−</sup>)<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>]·4CH<sub>3</sub>OH·56H<sub>2</sub>O (<b>1</b>) and [Cu<sub>4</sub>(L<sup>3−</sup>)<sub>2</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), dinuclear [Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(N<sub>3</sub>)(H<sub>2</sub>O)(NO<sub>3</sub>)] (<b>3</b>), polynuclear {[Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(H<sub>2</sub>O)(BF<sub>4</sub>)(N<sub>3</sub>)]·H<sub>2</sub>O}<sub>n</sub> (<b>4</b>), heptanuclear [Cu<sub>7</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>2</sub>(O)<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>6</sub>]·6CH<sub>3</sub>OH·44H<sub>2</sub>O (<b>5</b>), and decanuclear [Cu<sub>10</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>4</sub>(O)<sub>2</sub>(OH)<b><sub>2</sub></b>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>4</sub>] (C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>2</sub>·20H<sub>2</sub>O (<b>6</b>). X-ray studies have revealed that the basic building block in <b>1</b>, <b>3</b>, and <b>4</b> is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL<sup>2−</sup> or H<sub>3</sub>L1<sup>2−</sup>, and one μ-1,1-azido (N<sub>3</sub><sup>−</sup>) ion and in <b>2</b>, <b>5</b>, and <b>6</b> by μ-phenoxide oxygen of L<sup>3−</sup> or H<sub>3</sub>L1<sup>2−</sup> and μ-O<sup>2−</sup> or μ<sub>3</sub>-O<sup>2−</sup> ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (<b>1</b> and <b>6</b>), 2D-sheets (<b>3</b>), and 3D-structures (<b>4</b>). In <b>5</b>, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In <b>1</b>, <b>3</b>, and <b>5,</b> Cu(II) ions in [Cu<sub>2</sub>] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm<sup>−1</sup>.https://www.mdpi.com/1420-3049/25/23/5549self-assembly of supramolecular architecturesantiferromagnetically-coupled copper(II) complexesmagneto-structural correlationsphenolate and azido bridged copper(II) complexes
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Santokh S. Tandon Scott D. Bunge Neil Patel Esther C. Wang Laurence K. Thompson
spellingShingle	Santokh S. Tandon Scott D. Bunge Neil Patel Esther C. Wang Laurence K. Thompson Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities Molecules self-assembly of supramolecular architectures antiferromagnetically-coupled copper(II) complexes magneto-structural correlations phenolate and azido bridged copper(II) complexes
author_facet	Santokh S. Tandon Scott D. Bunge Neil Patel Esther C. Wang Laurence K. Thompson
author_sort	Santokh S. Tandon
title	Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities
title_short	Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities
title_full	Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities
title_fullStr	Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities
title_full_unstemmed	Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities
title_sort	self-assembly of antiferromagnetically-coupled copper(ii) supramolecular architectures with diverse structural complexities
publisher	MDPI AG
series	Molecules
issn	1420-3049
publishDate	2020-11-01
description	The self-assembly of 2,6-diformyl-4-methylphenol (<b>DFMP</b>) and 1-amino-2-propanol (<b>AP</b>)/2-amino-1,3-propanediol (<b>APD</b>) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H<sub>3</sub>L and H<sub>5</sub>L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu<sub>4</sub>(HL<sup>2−</sup>)<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>]·4CH<sub>3</sub>OH·56H<sub>2</sub>O (<b>1</b>) and [Cu<sub>4</sub>(L<sup>3−</sup>)<sub>2</sub>(OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), dinuclear [Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(N<sub>3</sub>)(H<sub>2</sub>O)(NO<sub>3</sub>)] (<b>3</b>), polynuclear {[Cu<sub>2</sub>(H<sub>3</sub>L1<sup>2−</sup>)(H<sub>2</sub>O)(BF<sub>4</sub>)(N<sub>3</sub>)]·H<sub>2</sub>O}<sub>n</sub> (<b>4</b>), heptanuclear [Cu<sub>7</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>2</sub>(O)<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>6</sub>]·6CH<sub>3</sub>OH·44H<sub>2</sub>O (<b>5</b>), and decanuclear [Cu<sub>10</sub>(H<sub>3</sub>L1<sup>2−</sup>)<sub>4</sub>(O)<sub>2</sub>(OH)<b><sub>2</sub></b>(C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>4</sub>] (C<sub>6</sub>H<sub>5</sub>CO<sub>2</sub>)<sub>2</sub>·20H<sub>2</sub>O (<b>6</b>). X-ray studies have revealed that the basic building block in <b>1</b>, <b>3</b>, and <b>4</b> is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL<sup>2−</sup> or H<sub>3</sub>L1<sup>2−</sup>, and one μ-1,1-azido (N<sub>3</sub><sup>−</sup>) ion and in <b>2</b>, <b>5</b>, and <b>6</b> by μ-phenoxide oxygen of L<sup>3−</sup> or H<sub>3</sub>L1<sup>2−</sup> and μ-O<sup>2−</sup> or μ<sub>3</sub>-O<sup>2−</sup> ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (<b>1</b> and <b>6</b>), 2D-sheets (<b>3</b>), and 3D-structures (<b>4</b>). In <b>5</b>, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In <b>1</b>, <b>3</b>, and <b>5,</b> Cu(II) ions in [Cu<sub>2</sub>] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm<sup>−1</sup>.
topic	self-assembly of supramolecular architectures antiferromagnetically-coupled copper(II) complexes magneto-structural correlations phenolate and azido bridged copper(II) complexes
url	https://www.mdpi.com/1420-3049/25/23/5549
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Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

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