Touching the upper limit for ferromagnetic interactions in hetero-bridged dinuclear [Cu2II] complexes using a novel N5-dinucleating ligand bearing an endogenous monoatomic amido(R–NH−)-bridging group

Colacio, Enrique; Perea‐Buceta, Jesus E.; Mota, Antonio J.; Brechin, Euan K.; Prescimone, Alessandro; Hänninen, Mikko M.; Seppälä, Petri; Sillanpää, Reijo

doi:10.1039/c1cc16590a

Cited by 13 publications

(2 citation statements)

References 25 publications

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“…For comparison, the closest Cu–Cu distance in crystalline CuO is 2.91 Å . Despite the Columbic repulsion between the two Cu(II) ions, few analogous dinuclear organometallic Cu(II) complexes were also reported and their internuclear distances were around 2.95–3.03 Å as characterized by X-ray crystallography. − Thus, the present optimized geometries for the gas-phase [(Cu(II)) 2 ( S -naproxen)( l -His) 2 –3H] + with short Cu–Cu distance are reasonable.…”

Section: Results and Discussionmentioning

confidence: 80%

Self-Assembled Binuclear Cu(II)–Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry

Chau

Tang

et al. 2018

Anal. Chem.

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Naproxen is one of the most consumed nonsteroidal anti-inflammatory drugs and marketed as S-naproxen since R-naproxen is hepatotoxic. In this study, chiral recognition of naproxen has been investigated by tandem mass spectrometry (MS/MS). Among all diastereomeric complexes formed between naproxen and the examined chiral selectors, including cyclodextrins (α/β/γ-CD), modified phenylalanines ( N-acetyl-phenylalanine, N-t-butoxycarbonyl-phenylalanine, N-9-fluorenylmethyloxycarbonyl-phenylalanine), amino acids (Trp, Phe, Tyr, His), glucose, tartaric acid, and vancomycin, a novel binuclear metal bound diastereomeric complexes [(M(II))( S/ R-naproxen)(l-His)-3H] (M = Cu, Ni, or Co with Cu being the best) could allow effective identification of the absolute configuration of naproxen and determination of its enantiomeric excess ( ee) through MS/MS analysis. The key candidate structure of [(Cu(II))( S/ R-naproxen)(l-His)-3H] has been revealed by means of collision-induced dissociation, ion mobility mass spectrometry and density functional theory calculations, indicating an interesting and unusual self-assembled compact geometry with the two Cu(II) ions bridged closely together (Cu-Cu distance is 3.04 Å) by the carboxylate groups of the two histidines. It was shown that the difference in dissociation efficiency between the two diastereomers was attributed to the interaction between the NH bond of the amino group of one histidine and the naphthyl ring of naproxen. The present report is the first to observe and characterize the complex of (Cu(II))(His) with aromatic acid, which could contribute to the chiral recognition of other chiral aromatic acids, design of catalysts based on binuclear copper bound complex, as well as the better understanding of metal ion complexation by His or His-containing ligands.

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Section: Results and Discussionmentioning

confidence: 80%

Self-Assembled Binuclear Cu(II)–Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry

Chau

Tang

et al. 2018

Anal. Chem.

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“…To the best of our knowledge, the tridentate bridging coordination of deprotonated abpt‐H (or normal abpt) ligand has never been observed before, although tetradentate coordination (either through two pyridyl and two triazole nitrogen atoms, or less typically through bidentate amine and two pyridyl nitrogen atoms) with bridging function is known , . Moreover, the last type of tetradentate coordination was also observed in three Cu II complexes with related 4‐amino‐3,5‐bis(bipyridine‐2‐yl)‐1,2,4‐triazole ligand (abbt) in which two additional nitrogen atoms from bipyridine moieties are coordinated too, thus the abbt ligand is hexacoordinate . Both cobalt ions in 2 have distorted octahedral [CoN 6 ] environment with cis N–Co–N angles ranging from 79.22(9) to 97.96(8)° (Table ).…”

Section: Resultsmentioning

confidence: 89%

New Cobalt(II) Field‐Induced Single‐Molecule Magnet and the First Example of a Cobalt(III) Complex with Tridentate Binding of a Deprotonated 4‐Amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐Triazole Ligand

et al. 2018

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From Co(NO3)2·6H2O ‐ NaN3 ‐ abpt reaction system, a mononuclear complex [Co(abpt)2(N3)2] (abpt = 4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole) (1) and a dinuclear complex [Co2(abpt)(µ‐abpt‐H)2(N3)4]·1.12H2O (2) were obtained. The presence of neutral abpt, as well as azido ligands was proved by IR spectroscopy. X‐ray crystallography shows that 1 is a molecular CoII complex with two azido ligands coordinated in trans‐positions, while 2 is a dinuclear CoIII complex bridged by two abpt‐H ligands. π–π stacking interactions between pyridyl rings of abpt and N‐H···N and C‐H···N hydrogen bonds in 1 and 2 stabilize their structures by creating a 3D supramolecular network. The analysis of the magnetic properties of 1 revealed negative zero‐field splitting parameter D = –24.1 cm–1 supported also by CASSCF/NEVPT2 and CASSCF/CASPT2 theoretical calculations. The X‐band electron paramagnetic resonance also gives an evidence for a strong rhombic character of the anisotropy. The investigation of the ac susceptibility measurements identified 1 as a field‐induced single‐molecule magnet, in which direct, Raman and Orbach relaxation processes are present.

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Intramolecular and Intermolecular Magnetic Coupling Mechanism of a Dinuclear Copper(II) Complex

Liu

Wei

et al. 2012

Zeitschrift anorg allge chemie

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A new dinuclear complex, [Cu 2 (μ 1,3 -NCS) 2 (Ophen) 2 (OH 2 ) 2 ], (HOphen = 1,10-phenanthrolin-2-ol) was synthesized and its crystal structure was determined by X-ray crystallography. In the complex, the Cu II ion assumes a distorted square pyramidal arrangement and the thiocyanate anion functions as bridged ligand and Ophen as capped ligand. The analysis of the crystal structure shows that there exists a ππ stacking interaction between the adjacent complexes. The theoretical calculations reveal that the magnetic coupling pathways from the thiocyanate anions bridge ligand and the π-π stacking magnetic coupling pathway resulted in the weak ferromagnetic interactions with 2J = 18.46 cm -1 and 2J = 10.46 cm -1 , respectively. The calculations also 181 display that the spin delocalization and the spin polarization occur in the bridge magnetic coupling system and the π-π stacking magnetic coupling system, and the magnetic coupling mechanism of the π-π stacking can be explained with McConnell I spin-polarization mechanism. The fitting for the data of the variable-temperature magnetic susceptibility with dinuclear Cu II formula gave the magnetic coupling constant 2J = 2.84 cm -1 and zJЈ = 0.03 cm -1 , in which the 2J = 2.84 cm -1 is attributed to the magnetic coupling from the bridge dinuclear Cu II unit and the zJЈ = 0.03 cm -1 is ascribed to the π-π stacking magnetic coupling system. The study may benefit to understand the magnetic coupling mechanism of π-π stacking system.

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Touching the upper limit for ferromagnetic interactions in hetero-bridged dinuclear [Cu₂^II] complexes using a novel N₅-dinucleating ligand bearing an endogenous monoatomic amido(R–NH⁻)-bridging group

Abstract: A novel N(5)-dinucleating ligand 4-amino-3,5-bis(bipyridine-2-yl)-1,2,4-triazole allows the preparation for the first time, and under mild conditions, of single and mixed amido(R-NH(-))-bridged copper(II) complexes, the latter exhibiting very strong ferromagnetic coupling.

Cited by 13 publications

References 25 publications

Self-Assembled Binuclear Cu(II)–Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry

Self-Assembled Binuclear Cu(II)–Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry

New Cobalt(II) Field‐Induced Single‐Molecule Magnet and the First Example of a Cobalt(III) Complex with Tridentate Binding of a Deprotonated 4‐Amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐Triazole Ligand

Intramolecular and Intermolecular Magnetic Coupling Mechanism of a Dinuclear Copper(II) Complex

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