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

Yulia A. Getmanenko; Christopher S. Mullins; Vladimir N. Nesterov; Stephanie Lake; Chad Risko; Ezekiel Johnston-Halperin

doi:10.1039/c8ra05697h

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

Yulia A. Getmanenko, Christopher S. Mullins, Vladimir N. Nesterov, Stephanie Lake, Chad Risko, Ezekiel Johnston-Halperin

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

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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 T_C 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 tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]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 π 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.

Original language	English
Pages (from-to)	36223-36232
Number of pages	10
Journal	RSC Advances
Volume	8
Issue number	63
DOIs	https://doi.org/10.1039/c8ra05697h
State	Published - 2018

Bibliographical note

Funding Information:
This work was supported by the Center for Emergent Materials, an NSF MRSEC under award number DMR-1420451, NSF DMR-1523611, and Infrastructure Seed Award (NSF Grant #IIA-1301346). We acknowledge the NSF MRI Program (CHE-1726652) and the UNT for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. Y. A. G. thanks Professor Yang Qin (University of New Mexico) for providing synthetic facilities for the preparation of the ligand and for helpful discussions, Dr Camelia Selcu (The Ohio State University) for assistance with the SQUID measurements, Dr Tanya Whitmer for assistance with NMR experiment (The Ohio State University), and Mr Michael Chilcote and Mr Andrew Franson for helpful discussions. The computational work at the University of Kentucky (UK) was supported in part by start-up funds received from the UK Vice President for Research and the UK Center for Applied Energy Research (CAER). Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS).

Publisher Copyright:
© 2018 The Royal Society of Chemistry.

ASJC Scopus subject areas

Chemistry (all)
Chemical Engineering (all)

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

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 tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]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 π 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.",

author = "Getmanenko, {Yulia A.} and Mullins, {Christopher S.} and Nesterov, {Vladimir N.} and Stephanie Lake and Chad Risko and Ezekiel Johnston-Halperin",

note = "Funding Information: This work was supported by the Center for Emergent Materials, an NSF MRSEC under award number DMR-1420451, NSF DMR-1523611, and Infrastructure Seed Award (NSF Grant #IIA-1301346). We acknowledge the NSF MRI Program (CHE-1726652) and the UNT for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. Y. A. G. thanks Professor Yang Qin (University of New Mexico) for providing synthetic facilities for the preparation of the ligand and for helpful discussions, Dr Camelia Selcu (The Ohio State University) for assistance with the SQUID measurements, Dr Tanya Whitmer for assistance with NMR experiment (The Ohio State University), and Mr Michael Chilcote and Mr Andrew Franson for helpful discussions. The computational work at the University of Kentucky (UK) was supported in part by start-up funds received from the UK Vice President for Research and the UK Center for Applied Energy Research (CAER). Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c8ra05697h",

language = "English",

volume = "8",

pages = "36223--36232",

number = "63",

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T1 - Magnetic ordering in a vanadium-organic coordination polymer using a pyrrolo[2,3-

T2 - D:5,4- d ′]bis(thiazole)-based ligand

AU - Getmanenko, Yulia A.

AU - Mullins, Christopher S.

AU - Nesterov, Vladimir N.

AU - Lake, Stephanie

AU - Risko, Chad

AU - Johnston-Halperin, Ezekiel

N1 - Funding Information: This work was supported by the Center for Emergent Materials, an NSF MRSEC under award number DMR-1420451, NSF DMR-1523611, and Infrastructure Seed Award (NSF Grant #IIA-1301346). We acknowledge the NSF MRI Program (CHE-1726652) and the UNT for supporting the acquisition of the Rigaku XtaLAB Synergy-S X-ray diffractometer. Y. A. G. thanks Professor Yang Qin (University of New Mexico) for providing synthetic facilities for the preparation of the ligand and for helpful discussions, Dr Camelia Selcu (The Ohio State University) for assistance with the SQUID measurements, Dr Tanya Whitmer for assistance with NMR experiment (The Ohio State University), and Mr Michael Chilcote and Mr Andrew Franson for helpful discussions. The computational work at the University of Kentucky (UK) was supported in part by start-up funds received from the UK Vice President for Research and the UK Center for Applied Energy Research (CAER). Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018

Y1 - 2018

N2 - 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 tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]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 π 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.

AB - 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 tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]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 π 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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Magnetic ordering in a vanadium-organic coordination polymer using a pyrrolo[2,3-: D:5,4- d ′]bis(thiazole)-based ligand

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