Experimental and theoretical studies on the magnetic properties of manganese(II) compounds with mixed isocyanate and carboxylate bridges

Yu Ma; Nuno A.G. Bandeira; Vincent Robert; En Qing Gao

doi:10.1002/chem.201002243

Experimental and theoretical studies on the magnetic properties of manganese(II) compounds with mixed isocyanate and carboxylate bridges

Yu Ma
, Nuno A.G. Bandeira
, Vincent Robert^*
, En Qing Gao

^*Corresponding author for this work

School of Chemistry and Molecular Engineering

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

26 Scopus citations

Abstract

Two manganese(II) isocyanate complexes with different flexible zwitterionic dicarboxylate ligands, [Mn₂(bcpp)(NCO)₄]_n (1; bcpp=1,3-bis(N-carboxylatomethyl-4-pyridinio)propane) and [Mn ₂(bcp)(NCO)₄]_n (2; bcp=bis(N-carboxylatomethyl) -4,4′-bipyridinium, have been synthesized and characterized by X-ray crystallography and magnetic measurements. Both compounds consist of two-dimensional coordination layers in which uniform anionic chains with mixed (NCO)₂(COO) triple bridges are cross-linked by flexible cationic 4,4′-trimethylenedipyridinium spacers. Magnetic studies revealed antiferromagnetic interactions through the triple bridges (J=-8.0a cm ^-1 (1) and J=-8.6a cm^-1 (2)), which are stronger than those in the isoelectronic analogue (N₃)₂(COO). To complement the experimental data, periodic and finite-cluster DFT and CASPT2 calculations were performed on the dimeric units of the (NCO)₂(COO) and (N₃)₂(COO) mixed-bridged systems to support the Heisenberg picture and stress the relative efficiency of the magnetic couplers. It was found that the isocyanate ligand plays a greater role in the conveyance of antiferromagnetic behavior than the azide counterpart, and that both pseudohalide bridges function cooperatively with the carboxylate group.

Original language	English
Pages (from-to)	1988-1998
Number of pages	11
Journal	Chemistry - A European Journal
Volume	17
Issue number	6
DOIs	https://doi.org/10.1002/chem.201002243
State	Published - 7 Dec 2011

Keywords

bridging ligands
carboxylate ligands
density functional calculations
magnetic properties
manganese

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@article{98bb11e98f194efdada89de35fdc9d6d,

title = "Experimental and theoretical studies on the magnetic properties of manganese(II) compounds with mixed isocyanate and carboxylate bridges",

abstract = "Two manganese(II) isocyanate complexes with different flexible zwitterionic dicarboxylate ligands, [Mn2(bcpp)(NCO)4]n (1; bcpp=1,3-bis(N-carboxylatomethyl-4-pyridinio)propane) and [Mn 2(bcp)(NCO)4]n (2; bcp=bis(N-carboxylatomethyl) -4,4′-bipyridinium, have been synthesized and characterized by X-ray crystallography and magnetic measurements. Both compounds consist of two-dimensional coordination layers in which uniform anionic chains with mixed (NCO)2(COO) triple bridges are cross-linked by flexible cationic 4,4′-trimethylenedipyridinium spacers. Magnetic studies revealed antiferromagnetic interactions through the triple bridges (J=-8.0a cm -1 (1) and J=-8.6a cm-1 (2)), which are stronger than those in the isoelectronic analogue (N3)2(COO). To complement the experimental data, periodic and finite-cluster DFT and CASPT2 calculations were performed on the dimeric units of the (NCO)2(COO) and (N3)2(COO) mixed-bridged systems to support the Heisenberg picture and stress the relative efficiency of the magnetic couplers. It was found that the isocyanate ligand plays a greater role in the conveyance of antiferromagnetic behavior than the azide counterpart, and that both pseudohalide bridges function cooperatively with the carboxylate group.",

keywords = "bridging ligands, carboxylate ligands, density functional calculations, magnetic properties, manganese",

author = "Yu Ma and Bandeira, \{Nuno A.G.\} and Vincent Robert and Gao, \{En Qing\}",

year = "2011",

month = dec,

day = "7",

doi = "10.1002/chem.201002243",

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T1 - Experimental and theoretical studies on the magnetic properties of manganese(II) compounds with mixed isocyanate and carboxylate bridges

AU - Ma, Yu

AU - Bandeira, Nuno A.G.

AU - Robert, Vincent

AU - Gao, En Qing

PY - 2011/12/7

Y1 - 2011/12/7

N2 - Two manganese(II) isocyanate complexes with different flexible zwitterionic dicarboxylate ligands, [Mn2(bcpp)(NCO)4]n (1; bcpp=1,3-bis(N-carboxylatomethyl-4-pyridinio)propane) and [Mn 2(bcp)(NCO)4]n (2; bcp=bis(N-carboxylatomethyl) -4,4′-bipyridinium, have been synthesized and characterized by X-ray crystallography and magnetic measurements. Both compounds consist of two-dimensional coordination layers in which uniform anionic chains with mixed (NCO)2(COO) triple bridges are cross-linked by flexible cationic 4,4′-trimethylenedipyridinium spacers. Magnetic studies revealed antiferromagnetic interactions through the triple bridges (J=-8.0a cm -1 (1) and J=-8.6a cm-1 (2)), which are stronger than those in the isoelectronic analogue (N3)2(COO). To complement the experimental data, periodic and finite-cluster DFT and CASPT2 calculations were performed on the dimeric units of the (NCO)2(COO) and (N3)2(COO) mixed-bridged systems to support the Heisenberg picture and stress the relative efficiency of the magnetic couplers. It was found that the isocyanate ligand plays a greater role in the conveyance of antiferromagnetic behavior than the azide counterpart, and that both pseudohalide bridges function cooperatively with the carboxylate group.

AB - Two manganese(II) isocyanate complexes with different flexible zwitterionic dicarboxylate ligands, [Mn2(bcpp)(NCO)4]n (1; bcpp=1,3-bis(N-carboxylatomethyl-4-pyridinio)propane) and [Mn 2(bcp)(NCO)4]n (2; bcp=bis(N-carboxylatomethyl) -4,4′-bipyridinium, have been synthesized and characterized by X-ray crystallography and magnetic measurements. Both compounds consist of two-dimensional coordination layers in which uniform anionic chains with mixed (NCO)2(COO) triple bridges are cross-linked by flexible cationic 4,4′-trimethylenedipyridinium spacers. Magnetic studies revealed antiferromagnetic interactions through the triple bridges (J=-8.0a cm -1 (1) and J=-8.6a cm-1 (2)), which are stronger than those in the isoelectronic analogue (N3)2(COO). To complement the experimental data, periodic and finite-cluster DFT and CASPT2 calculations were performed on the dimeric units of the (NCO)2(COO) and (N3)2(COO) mixed-bridged systems to support the Heisenberg picture and stress the relative efficiency of the magnetic couplers. It was found that the isocyanate ligand plays a greater role in the conveyance of antiferromagnetic behavior than the azide counterpart, and that both pseudohalide bridges function cooperatively with the carboxylate group.

KW - bridging ligands

KW - carboxylate ligands

KW - density functional calculations

KW - magnetic properties

KW - manganese

UR - https://www.scopus.com/pages/publications/79551478160

U2 - 10.1002/chem.201002243

DO - 10.1002/chem.201002243

M3 - 文章

AN - SCOPUS:79551478160

SN - 0947-6539

VL - 17

SP - 1988

EP - 1998

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 6

ER -

Experimental and theoretical studies on the magnetic properties of manganese(II) compounds with mixed isocyanate and carboxylate bridges

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Keywords

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