Mono‐ and Di‐chloro‐bridged Discrete Dimers and Trimers and Mono‐Chloro‐Bridged 1D‐Coordination Polymer of Copper(II). Magneto‐structural Studies12. Issue 6 (7th March 2014)

• Record Type: Journal Article
• Authors: Singh, Ravindra; Lloret, Francesc; Mukherjee, Rabindranath
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 640:Issue 6(2014)
• Page Start: 1086
• Page End: 1094
• Publication Date: 2014-03-07
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400005
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p> The synthesis, structural characterization, and magnetic properties of three copper(II) complexes, a mono‐chloro‐bridged [Cu<sub>2</sub><sup>II</sup>(L<sup>6</sup>)<sub>2</sub>(μ‐Cl)(Cl)(Cu<sup>II</sup>Cl<sub>4</sub>)] (<bold>1</bold>) and a dichloro‐bridged [Cu<sup>II</sup><sub>2</sub>(L<sup>7</sup>)<sub>2</sub>(μ‐Cl)<sub>2</sub>][ClO<sub>4</sub>]<sub>2</sub> (<bold>3</bold>) discrete trimers and dimers, and a mono‐chloro‐bridged 1D‐coordination polymer [Cu<sup>II</sup>(L<sup>6</sup>)(μ‐Cl)][ClO<sub>4</sub>]<bold>·</bold>CH<sub>3</sub>CN (<bold>2</bold>), are reported. Molecular structures were authenticated by X‐ray crystallography. Temperature‐dependent magnetic measurements carried out on powdered samples of <bold>1</bold>–<bold>3</bold> indicated a very weak antiferromagnetic exchange‐coupling within the {Cu<sup>II</sup>(μ‐Cl)Cu<sup>II</sup>(μ‐Cl)Cu<sup>II</sup>Cl<sub>3</sub>}<sup>+</sup> units in <bold>1</bold> [Curie‐Weiss plot: <italic>θ</italic> = –0.19(1) K and <italic>g</italic> = 2.07(1)], a ferromagnetic behavior within {Cu<sup>II</sup>(μ‐Cl)<sub>2</sub>Cu<sup>II</sup>}<sup>2+</sup> units in <bold>3</bold> [<italic>Ĥ</italic> = –<italic>JS</italic><sub>1</sub><bold>·</bold><italic>S</italic><sub>2</sub>: <italic>J</italic> = +6.0(1) cm<sup>–1</sup>, <italic>D</italic> (zero‐field splitting parameter) = 4.5(2) cm<sup>–1</sup>, and <italic>g</italic> = 2.11], and a weak intrachain antiferromagnetic behavior due to {Cu<sup>II</sup>(μ‐Cl)Cu<sup>II</sup>}<sup>3+</sup> units in <bold>2</bold> [single‐chain polymer: <italic>J</italic> = –0.20(1) cm<sup>–1</sup> and <italic>g</italic> = 2.11]. The square‐pyramidal stereochemistry of the central copper(II) atoms in <bold>1</bold>–<bold>3</bold> was identified by their absorption spectral properties in acetontrile. An attempt was made to rationalize the observed magneto‐structural behavior.</p> </abstract>