Co(<scp>ii</scp>)-Based single-ion magnets with 1,1′-ferrocenediyl-bis(diphenylphosphine) metalloligands

Hrubý, J.; Dvorak, Denis; Squillantini, Lorenzo; Mannini, Matteo; Slageren, Joris van; Herchel, Radovan; Němec, Ivan; Neugebauer, Petr

doi:10.1039/d0dt01512a

Cited by 14 publications

(11 citation statements)

References 88 publications

(29 reference statements)

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“…Moreover, for some molecular systems, wet lithography may be a more reasonable option for maintaining their magnetic properties, as it allows for the transfer of the molecules onto substrates directly via chemical crafting from a solution. 11 Co(II) complexes with 2,6-bis(benzimidazole-1-yl)pyridine (bbp) tridentate ligands are a well-known family of fieldinduced SIMs, where their rigid and aromatic ligand skeleton favours geometries supporting higher magnetic anisotropy, thus inducing a large zero-field splitting parameter D. 12,13 Furthermore, the rationalised introduction of aromatic or aliphatic substituents on the ligand skeleton has a significant impact on the relaxation mechanisms, which can be realized through single or multiple relaxation channels. 7,14 Our recent reports were focused on the pentacoordinate Co(II)-SIMs with bbp ligands functionalised by long aliphatic chains.…”

Section: Introductionmentioning

confidence: 99%

Neutral cobalt(ii)-bis(benzimidazole)pyridine field-induced single-ion magnets for surface deposition

Juráková

Fellner

Schlittenhardt

et al. 2023

Inorg. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

Neutral cobalt(ii)-bis(benzimidazole)pyridine field-induced single-ion magnets for surface deposition

Juráková

Fellner

Schlittenhardt

et al. 2023

Inorg. Chem. Front.

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“…The magnetic properties of magnetic molecules can be precisely measured by high-frequency electron spin resonance (HF-ESR) both in bulk [11][12][13][14][15][16][17][18][19][20] and on a surface [21][22][23]. Primarily, the Zeeman and zero-field-splitting (ZFS) contributions to the spin Hamiltonian with information about the intrinsic magnetic properties of a molecule can be determined.…”

Section: Introductionmentioning

confidence: 99%

Deposition of Tetracoordinate Co(II) Complex with Chalcone Ligands on Graphene

et al. 2020

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Studying the properties of complex molecules on surfaces is still mostly an unexplored research area because the deposition of the metal complexes has many pitfalls. Herein, we probed the possibility to produce surface hybrids by depositing a Co(II)-based complex with chalcone ligands on chemical vapor deposition (CVD)-grown graphene by a wet-chemistry approach and by thermal sublimation under high vacuum. Samples were characterized by high-frequency electron spin resonance (HF-ESR), XPS, Raman spectroscopy, atomic force microscopy (AFM), and optical microscopy, supported with density functional theory (DFT) and complete active space self-consistent field (CASSCF)/N-electron valence second-order perturbation theory (NEVPT2) calculations. This compound’s rationale is its structure, with several aromatic rings for weak binding and possible favorable π–π stacking onto graphene. In contrast to expectations, we observed the formation of nanodroplets on graphene for a drop-cast sample and microcrystallites localized at grain boundaries and defects after thermal sublimation.

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“…The field of SMMs started with mixed-valent Mn 12 acetate, and the first Co II -based SMM was a tetrametallic complex [Co 4 (hmp) 4 ] [hmp = hydroxymethylpyridine], while the first example of Co II SIM was a penta-coordinate complex having a square-pyramidal geometry with an acyclic N3 ligand along with two [NCS] − coligands . Though quite a few Co II -based SMMs/SIMs have been reported in numerous coordination environments over the past few years, ,− still, it is challenging to stabilize a lower coordinated Co(II) SIM, as the high-spin Co(II) favors the octahedral coordination environment. − …”

Section: Introductionmentioning

confidence: 99%

Tuning of Dimensionality and Nuclearity as a Function of Ligand Field Modulation Resulting in Field-Induced Cobalt(II) Single-Ion Magnet

Hossain

Kamilya

Ghosh

et al. 2023

Crystal Growth & Design

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The present study reveals that predetermined diverse topology and desired properties can be achieved by strategically designing the ligand and it confirms that the structural and magnetic features of cobalt(II) complexes have a significant impact of the ligand modulation and proper utilization of a coligand. In this work, tactically, two new Pyclen-based macrocyclic N4 ligands have been designed to demonstrate the effect of the ligand field on structure and magnetic properties. Using these macrocyclic N4 ligands, a series of cobalt complexes, 2), and [Co(L2−N4)(NCS) 2 ] (3), have been synthesized and characterized by different physicochemical techniques, including singlecrystal X-ray diffraction, magnetic, and various spectroscopic methods. The dinuclear plus mononuclear (2 + 1) cobalt complex (1) and 2D cobalt coordination polymer (2) are synthesized using the same macrocyclic N4 ligand: 3,6,9-trimethyl-3,6,9-triaza-1(2,6)pyridinacyclodecaphane (L1−N4) with a variation of coligand from thiocyanato to dicyananamido. A penta-coordinated mononuclear cobalt complex (3) is synthesized by substituting one methyl group of L1−N4 with a carboxaldehyde group, which leads to a [3,9-dimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane-6-carbaldehyde (L2−N4)] ligand. Single-crystal X-ray diffraction studies reveal the impact of strategic modification of ligands and variation of coligand on the coordination environment, dimensionality, and topology of Co(II) complexes. Whereas, detailed magnetic studies disclose the occurrence of Co(II) ions in a high-spin electronic state for all three complexes, yet, only complex 3 displays exciting slow relaxation of magnetization using an external dc magnetic field and acts as a single-ion magnet, while complexes 1 and 2 display no such property. Detailed theoretical studies have been carried out to better understand and justify the experimentally obtained result.

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Co(ii)-Based single-ion magnets with 1,1′-ferrocenediyl-bis(diphenylphosphine) metalloligands

Abstract: Two tetracoordinate Co(ii)-based single-ion-magnets were synthesised and characterised by HF-ESR, XPS, UV-VIS with support of ab initio quantum calculations and tested for drop-casting and sublimation depositions of thin films.

Cited by 14 publications

References 88 publications

Neutral cobalt(ii)-bis(benzimidazole)pyridine field-induced single-ion magnets for surface deposition

Neutral cobalt(ii)-bis(benzimidazole)pyridine field-induced single-ion magnets for surface deposition

Deposition of Tetracoordinate Co(II) Complex with Chalcone Ligands on Graphene

Tuning of Dimensionality and Nuclearity as a Function of Ligand Field Modulation Resulting in Field-Induced Cobalt(II) Single-Ion Magnet

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