Magnetic ordering in a vanadium-organic coordination polymer using a pyrrolo[2,3-d:5,4-d0] bis(thiazole)-based ligand

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This article presents the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature TC of ~110 K, a coercive field of ~5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)~₂ (V·(TCNE)~₂).

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Getmanenko, Yulia A.; Mullins, Christopher S.; Nesterov, Vladimir N.; Lake, Stephanie; Risko, Chad & Johnston-Halperin, Ezekiel October 11, 2018.

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This article presents the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature TC of ~110 K, a coercive field of ~5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)~₂ (V·(TCNE)~₂).

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10 p.

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Abstract: Here we present the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature TC of ~110 K, a coercive field of ~5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)~₂ (V·(TCNE)~₂).This material was prepared using a new tetracyanosubstituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d0]bis(thiazole) (C6-PBTz). Single crystal X-ray diffraction of the 2,6-diiodo derivative of the parent C6-PBTz, showed a disordered hexyl chain and a nearly linear arrangement of the substituents in positions 2 and 6 of the tricyclic core. Density functional theory (DFT) calculations indicate that C6-PBTz-based ligand 7 is a strong acceptor with an electron affinity larger than that of TCNE and several other ligands previously used in molecular magnets. This effect is due in part to the electron-deficient thiazole rings and extended delocalization of the frontier molecular orbitals. The ligand detailed in this study, a representative example of fused heterocycle aromatic cores with extended p conjugation, introduces new opportunities for structure–magnetic-property correlation studies where the chemistry of the tricyclic heterocycles can modulate the electronic properties and the substituent at the central N-position can vary the spatial characteristics of the magnetic polymer.

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  • RSC Advances, 2018. London, UK: Royal Society of Chemistry

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  • Publication Title: RSC Advances
  • Volume: 8
  • Page Start: 36223
  • Page End: 36232
  • Peer Reviewed: Yes

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  • October 11, 2018

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  • July 3, 2018

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  • October 11, 2018

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  • Nov. 28, 2018, 5:21 p.m.

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Getmanenko, Yulia A.; Mullins, Christopher S.; Nesterov, Vladimir N.; Lake, Stephanie; Risko, Chad & Johnston-Halperin, Ezekiel. Magnetic ordering in a vanadium-organic coordination polymer using a pyrrolo[2,3-d:5,4-d0] bis(thiazole)-based ligand, article, October 11, 2018; London, United Kingdom. (digital.library.unt.edu/ark:/67531/metadc1390621/: accessed December 18, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.