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1.
Inorg Chem ; 2020 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-32391690

RESUMO

Three mononuclear octahedral Co(II) complexes are reported, [Co(py)4(SCN)2] (1), [Co(py)4(Cl)2]·H2O (2), and [Co(py)4(Br)2] (3), that exhibit different distortions with compression (1) or elongation (2 and 3) of the axial positions. Easy plane magnetic anisotropy was confirmed by magnetic, HF-EPR, and computational studies for all complexes. Further analyses indicate that both the sign and magnitude of zero-field splitting parameters experience a significant change (D ≥ ±150 cm-1) by tuning of the axial and equatorial ligand field strength. Slow magnetic relaxation is observed for all compounds which is dominated by the Raman process involving both acoustic and optical phonons.

2.
Dalton Trans ; 2020 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-32348385

RESUMO

The 1,2-diaza-4-phospholide (dp-) dipotassium ate complexes of chromium(ii) {[(η1-N-3,5-tBu2dp)4Cr][(η5-(N,N,C,C,P))2-K(η1-O-THF)2]2} (5) and {[(η1-N-3,5-Ph2dp)4Cr][(η5-(N,N,C,C,P))2-K(η1-O-THF)2]2}∞ (6) were synthesized and characterized by X-ray single crystal structure analysis. Complex 5 with a near-square planar geometry at the chromium(ii) ion was unambiguously characterized by the high field electron paramagnetic resonance (HF-EPR) technique and magnetic measurements, revealing that it is a field-induced single-molecule magnet (SMM).

3.
iScience ; 23(3): 100926, 2020 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-32146324

RESUMO

Long decoherence time is a key consideration for molecular magnets in the application of the quantum computation. Although previous studies have shown that the local symmetry of spin carriers plays a crucial part in the spin-lattice relaxation process, its role in the spin decoherence is still unclear. Herein, two nine-coordinated capped square antiprism neodymium moieties [Nd(CO3)4H2O]5- with slightly different local symmetries, C1 versus C4 (1 and 2), are reported, which feature in the easy-plane magnetic anisotropy as shown by the high-frequency electron paramagnetic resonance (HF-EPR) studies. Detailed analysis of the relaxation time suggests that the phonon bottleneck effect is essential to the magnetic relaxation in the crystalline samples of 1 and 2. The 240 GHz Pulsed EPR studies show that the higher symmetry results in longer decoherence times, which is supported by the first principle calculations.

4.
J Am Chem Soc ; 142(14): 6649-6660, 2020 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-32176486

RESUMO

Strong Mn-Mn coupling interactions (dipole-dipole and spin-exchange), predominantly determined by statistically and apparently short Mn···Mn distances in traditional heavily Mn2+-doped semiconductors, can promote energy transfer within randomly positioned and close-knit Mn2+ pairs. However, the intrinsic mechanism on controlling Mn2+ emission efficiency is still elusive due to the lack of precise structure information on local tetrahedrally coordinated Mn2+ ions. Herein, a group of Mn2+-containing metal-chalcogenide open frameworks (MCOFs), built from [Mn4In16S35] nanoclusters (denoted T4-MnInS) with a precise [Mn4S] configuration and length-variable linkers, were prepared and selected as unique models to address the above-mentioned issues. MCOF-5 and MCOF-6 that contained a symmetrical [Mn4S] core with a D2d point group and relatively long Mn···Mn distance (∼3.9645 Å) exhibited obvious red emission, while no room-temperature PL emission was observed in MCOF-7 that contained an asymmetric [Mn4S] configuration with a C1 point group and relatively short Mn···Mn distance (∼3.9204 Å). The differences of Mn-Mn dipole-dipole and spin-exchange interactions were verified through transient photoluminescent spectroscopy, electron spin resonance (ESR), and magnetic measurements. Compared to MCOF-5 and MCOF-6 showing a narrower/stronger ESR signal and longer decay lifetime of microseconds, MCOF-7 displayed a much broader/weaker ESR signal and shorter decay lifetime of nanoseconds. The results demonstrated the dominant role of distance-directed Mn-Mn dipole-dipole interactions over symmetry-directed spin-exchange interactions in modulating PL quenching behavior of Mn2+ emission. More importantly, the reported work offers a new pathway to elucidate Mn2+-site-dependent photoluminescence regulation mechanism from the perspective of atomically precise nanoclusters.

5.
Dalton Trans ; 49(7): 2159-2167, 2020 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-31994553

RESUMO

The effect of screening the CoII moment of monomeric [CoIIL2(H2O)] (L = 8-hydroxyquinaldine), having a trigonal bipyramid coordination, by diamagnetic Zn in CoxZn1-x solid solutions on its magnetic relaxation was explored using ac-susceptibility, high-field electron-spin-resonance measurements and CASPT2 calculations. The retention of the crystal structure for all the solid solutions was demonstrated using single crystal diffraction. The dc-magnetization and theoretical fittings of the susceptibility for Co1 and Co0.1Zn0.9 gave a large zero-field-splitting (ZFS) D of 50 ± 6 cm-1, and very weak dipole interaction between the nearest neighbors, while EPR and calculations confirmed the positive sign of the axial component (D). Consistent parameters were obtained from experiments and theory. Importantly, only field-induced relaxation was observed for the samples with less than 50% Co and a gradual change in the barrier energy to moment reversal and relaxation times was observed between 11% and 20% Co, while both were enhanced for higher dilutions. The results establish a clear barrier for extending the longevity of the magnetism for this type of single-ion species by lowering the intramolecular interactions. The results suggest that the magnetic interaction persists up to the second sphere, that is, for a dilution of 1 in 9 (11% Co). Importantly, this method is applicable to all single-ion magnet systems, that is, the optimum dilution concentration to restrain the dipole field can be given only by the single crystal structure.

6.
Angew Chem Int Ed Engl ; 59(1): 286-294, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31638312

RESUMO

Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11-hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co3 HITP2 and Ni3 HITP2 are compared. Unpaired 3d electrons in Co3 HITP2 result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co3 HITP2 , showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four-electron for Co3 HITP2 to two-electron for Ni3 HITP2 . Rechargeable zinc-air batteries using Co3 HITP2 as the air cathode catalyst demonstrate excellent energy efficiency and stability.

7.
J Phys Condens Matter ; 32(10): 105702, 2020 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-31703232

RESUMO

Tuning of spin-orbit coupling and electron correlation effects in iridates by introducing electron or hole carriers can produce interesting physical phenomena. In this work, we experimentally investigate the electron/hole doping effect on magnetism and electrical transport in the canted antiferromagnetic (AFM) double perovskite La2ZnIrO6, where hole/electron doping are realized in two serial La2Zn1-x Li x IrO6 (0 ⩽ x ⩽ 0.35) and La2Zn1-y Ga y IrO6 (0 ⩽ y  ⩽ 0.3) compounds, respectively. The x-ray photoelectron spectroscopy (XPS) reveals the existence of Ir5+ and Ir3+ oxide states in the Li+ and Ga3+ doped La2ZnIrO6. The magnetic susceptibilities and electron spin resonance (ESR) results reveal different responses between the Ir5+(5d4) and Ir3+ (5d6) ions in doped La2ZnIrO6, the Ir5+ ions have Van-Vleck paramagnetic contribution contrast to the completely nonmagnetic Ir3+ ions. Moreover, the Li+ doping cause more dramatic suppression of transition temperature (T N) and net ferromagnetic (FM) moments. All the Li+/Ga3+ doped samples remain Mott insulating state well fitted by the variable-range-hopping (VRH) transport mechanism. As a comparison, hole-doping is more effective to enhance the electrical conductivity than the case of electron, suggesting possible asymmetry of density of states nearby the Fermi level.

8.
Inorg Chem ; 58(21): 14440-14448, 2019 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-31626540

RESUMO

The magnetic properties of single-molecule magnets can be controlled by external conditions such as light, pressure, and temperature. Among these conditions, photochemical control is the best approach due to the accessibility and rapid conduction of light. In this work, an Er(III)-based complex with photoactive ligand bpe, [Er(nat)3·MeOH·bpe] (1, bpe = 1,2-bis(2-pyridyl)ethylene, nat = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione), was synthesized. The auxiliary ligand nat and cyclized ligand bpe stacked reasonably in the crystal structure. Two molecules of 1 experienced the [2, 2]-cycloaddition reaction under the UV irradiation in the solid state and [{Er(nat)3MeOH}2(tpcb)] (2, tpcb = tetrakis(4-pyridyl)cyclobutane) was produced. The slight change in the structure around Er(III) ions leads to the different magnetic properties, which illustrates the photochemical control of the magnetic properties of single-molecule magnets.

9.
Inorg Chem ; 58(16): 10680-10685, 2019 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-31385512

RESUMO

We have synthesized a new spin-1/2 antiferromagnet, Y2Cu7(TeO3)6Cl6(OH)2, via a traditional hydrothermal method. This compound crystallizes in the triclinic crystal system with space group P1̅. The magnetic ions constitute a two-dimensional layered lattice with a novel topological structure in which the Cu4 clusters make up distorted diamond chains along the a axis and these chains are connected by the Cu3 trimers. The magnetic susceptibility and specific heat measurements show that the compound is antiferromagnetically ordered at TN = 4.1 K. This antiferromagnetic ordering is further supported by electron spin resonance (ESR) data. The magnetization curve presents a field-induced metamagnetic transition at 0.2 T, followed by a magnetization plateau within a wide magnetic field range from 7 T to at least 55 T, which corresponds to 3/7 of the saturated magnetization with g = 2.15 obtained from ESR. The possible mechanism for the magnetization plateau is discussed.

10.
J Phys Condens Matter ; 31(12): 125801, 2019 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-30605894

RESUMO

Ni3V2O8, regarded as an S = 1 kagome staircase lattice antiferromagnet, possesses a novel magnetic field-temperature phase diagram. Specifically, a half plateau region is observed in the high field magnetization curve for magnetic fields in the range of 11-19 T. This experimental observation is theoretically unexpected for a standard kagome lattice antiferromagnet, and consequently, the underlying magnetic structure is still unclear. Multi-frequency electron spin resonance results in this study strongly support a collinear magnetic arrangement at the half plateau region. The resonant modes can be well fit by only considering the antiferromagnetic interactions on a four-spin sublattice of the spine sites.

11.
Angew Chem Int Ed Engl ; 58(12): 3748-3753, 2019 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-30589197

RESUMO

A new free carbon radical was obtained in a microwave-assisted solvothermal reaction of the primary amine (1-methyl-1H-benzo[d]imidazol-2-yl)methanamine with FeCl3 ⋅6 H2 O in methanol at 140 °C. Through a combination of crystallography and electrospray ionization mass spectrometry, the reaction process was studied. The longest domino reaction includes 14 steps and forms up to 12 new covalent bonds (9 C-N and 3 C-C bonds) and 3 five-membered heterocycles. For the first time, the homolytic cleavage of a C-O bond was used to synthesize a triarylmethyl radical.

12.
Dalton Trans ; 47(46): 16596-16602, 2018 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-30417917

RESUMO

Although a great number of single-ion magnets (SIMs) and spin-crossover (SCO) compounds have been discovered, multifunctional materials with the combination of SCO and SIM properties are extremely scarce. Here magnetic studies have been carried out for a mononuclear, five-coordinate cobalt(ii) complex [Co(3,4-lut)4Br]Br (1) with square pyramidal geometry. Direct-current magnetic measurement confirms the spin transition between the S = 1/2 and 3/2 states in the range of 150-290 K with a small hysteresis loop. Frequency- and temperature-dependent alternating-current magnetic susceptibility reveals slow magnetization relaxation under an applied dc field of 3000 Oe. The work here presents the first instance of the five-coordinate mononuclear cobalt(ii)-based SIM exhibiting the thermally induced complete SCO.

13.
Dalton Trans ; 47(30): 10162-10171, 2018 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-30010170

RESUMO

Experimental and theoretical studies of magnetic anisotropy and relaxation behavior of six-coordinate tris(pivalato)-Co(ii) and -Ni(ii) complexes (NBu4)[M(piv)3] (piv = pivalate, M = Co, 1; M = Ni, 2), with a coordination configuration at the intermediate between an octahedron and a trigonal prism, are reported. Direct current magnetic data and high-frequency and -field EPR spectra (HFEPR) of 1 have been modeled by a general Hamiltonian considering the first-order orbital angular momentum, while the spin Hamiltonian was used to interpret the data of 2. Both 1 and 2 show easy-axis magnetic anisotropies, which are further supported by ab initio calculations. Alternating current (ac) magnetic susceptibilities reveal slow magnetic relaxation at an applied dc field of 0.1 T in 1, which is characteristic of a field-induced single-ion magnet (SIM), but 2 does not exhibit single-ion magnetic properties at 1.8 K. Detailed analyses of relaxation times show a dominant contribution of a Raman process for spin relaxation in 1.

14.
Inorg Chem ; 57(12): 7006-7014, 2018 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-29855183

RESUMO

By utilizing a flexible tetrapyridinate ligand, tetrakis(4-pyridyloxymethylene) methane(L), a novel multifunctional soft porous framework, [Co(NCS)2(L)]·2H2O·CH3OH (1), was constructed. This framework exhibits quick and selective solvatochromic and vapochromic behavior during a reversible crystal-to-amorphous-to-crystal (CAC) transformation. Importantly, the rapid CAC transition can selectively be triggered by methanol molecules, even at low concentrations of liquid or gaseous methanol. This reproducible transition can be monitored by single-crystal and power X-ray analysis, IR, and UV-vis, which all powerfully illustrate the selectivity and sensitivity of this system. In addition, the typical magnetic behavior of single ion magnets (SIMs) has been successfully introduced into this 3D framework, and the modified dynamic relaxations have been investigated via experimental and theoretical analysis. The consistent observations of both experimental and theoretical results support that the distortions of the metal coordination environments should be responsible for the finely tuned SIM behavior.

15.
Inorg Chem ; 57(13): 7757-7762, 2018 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-29905464

RESUMO

By utilizing the quinolinic derivative, 8-carboxymethoxy-2-carboxylicquinoline (L), five transition metal coordination complexes, [M(L)(H2O)3]·H2O] (M = Mn (1), Co (2)), [Ni(L)(H2O)2] (3), and {[M(L)](H2O)} n (M = Ni (4), Cu (5)), were synthesized by hydrothermal methods employing similar synthetic strategies. The crystal structures, magnetism and high-field EPR were characterized for the obtained compounds. 1-3 are mononuclear compounds. 1 and 2 have pentagonal bipyramidal geometry, while 4 and 5 exhibit one-dimensional zig-zag chain. Direct current magnetic and EPR studies demonstrate that compound 2 has large and positive D value (∼70.4 cm-1), indicating the easy plane magnetic anisotropies of 2. This D value is the largest one in the reported Co(II) complexes with pentagonal bipyramidal geometry. Field-induced slow magnetic relaxation behavior was observed for 2 by the dynamic ac magnetic susceptibility measurements. The dc magnetic susceptibility studies of 4 and 5 give similar weak MII-MII antiferromagnetic interactions ( J = -1.50 and -3.55 K for 4 and 5, respectively). High-field EPR results show that 4 can be considered as a quantum antiferromagnet.

16.
J Phys Condens Matter ; 30(26): 265802, 2018 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-29775179

RESUMO

The spin dynamics of the two-dimensional triangular-lattice antiferromagnet AgCrS2 is investigated by electron spin resonance (ESR) spectroscopy. The g-factor is found to show an unusual non-monotonously temperature dependent behavior, which, along with the super-Curie behavior observed in the ESR intensity data, provides clear evidence for the competition between ferromagnetic and antiferromagnetic fluctuations at temperatures well above T N. On approaching the Néel temperature T N from above, the linewidth is found to diverge. Such a divergent behavior could be well described by the Kawamura-Miyashita model due to Z2 type magnetic vortex-antivortex pairing, which is consistent with the expectation for a 2D Heisenberg magnetic system.

17.
Inorg Chem ; 57(6): 3151-3157, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29517227

RESUMO

A new two-dimensional (2D) fluorophosphate compound Na3Cu5(PO4)4F·4H2O with a Cu5 cluster has been synthesized using a conventional hydrothermal method. The compound crystallizes in the orthorhombic crystal system with space group Pnma. The 2D layered structure is formed by cap-like {Cu5(PO4)4F} building units consisting of a Cu4O12F cluster plus a residual cap Cu2+ ion. Magnetic susceptibility exhibits a broad maximum at T2 = 19.2 K due to low-dimensional character followed by a long-range antiferromagnetic ordering at T1 = 11.5 K, which is further confirmed by the specific heat data. High-field magnetization measurement demonstrates a 2/5 quantum magnetization plateau above 40 T. The ESR data indicate the presence of magnetic anisotropy, in accordance with the 2D structure of the system.

18.
Dalton Trans ; 47(8): 2506-2510, 2018 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-29384533

RESUMO

The coordination geometries of the Co(ii) site in the two complexes [Co(imidazole)6][BPh4]2·0.3CH3CN (1) and [Co(imidazole)6][NO3]2 (2) were observed to display the ideal symmetries Ci and D3d, respectively. Both complexes were shown to be field-induced single-ion magnets. The effective energy barrier was found to decrease as the local symmetry changed from low-symmetry Ci to high-symmetry D3d.

19.
Inorg Chem ; 57(5): 2577-2583, 2018 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-29465993

RESUMO

By utilizing a preselected functional ligand produced by 1 H-imidazole-4,5-dicarboxylic acid, three isostructural lanthanide coordination polymers (CPs), denoted as {[Ln2(OH)2(L)2]·(DMF)·(H2O)4} n (Ln = Gd (1), Eu (2), Dy (3); L = 1-(4-carboxybenzyl)imidazole-4-carboxylic acid), containing a 1D infinite [Ln4(OH)4] subchain have been successfully constructed. The highly connected mode between the multifunctional ligand and 1D building units is responsible for the exceptional chemical stability of three lanthanide CPs. In addition, a study of the magnetic properties reveals that 1 displays a large magnetic entropy change (-Δ Sm = 30.33 J kg-1 K-1 with T = 2 K and Δ H = 7 T). Furthermore, genetic algorithm and quantum Monte Carlo methods were combined to simulate the magnetic coupling parameters of compound 1, shedding light on the effect of linking bridges on magnetic propagation. 2 shows intense luminescence in the range of 350-710 nm. Comparably, magnetic studies of 3 reveal the existence of a metamagnetic transformation from an antiferromagnetic interaction to a ferromagnetic interaction along with a decrease in temperature. Through fitting of the results of HF-EPR measurements, a component of the g tensor is obtained, g|| = 16.4(5), indicating the large anisotropy of 3.

20.
Dalton Trans ; 46(47): 16663-16670, 2017 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-29168858

RESUMO

Herein, quasi-square planar CuII(Hmbm)Cl2 (CBC, Hmbm = (1-methyl-1H-benzo[d]imidazol-2-yl)methanol) was arranged in a pseudo orthogonal way to form Cl-bridged chains, and further ππ interactions resulted in distorted hexagonal layers. DFT calculations reveal a bond strength order of Cu-Cl > Cu-O/N ≫ CuCl. ESI-MS data reveal several small fragments from CBC, but oligomeric [Cu], [Cu], and [Cu] for non-zero in-source energies; MS data indicates the occurrence of several chemical processes, viz. splitting of the ligand, oligomerization, and redox reaction of alcohol to aldehyde and CuII to CuI. Gibbs free energies for the fragments were estimated using DFT. The magnetic susceptibility was modeled with the ferromagnetic coupling J(Cu-Cl2aCu) = +0.99(30) cm-1 and J'(ππ) = +0.35(16) cm-1 and g = 2.38(2). HF-EPR determined the anisotropic g-values, gx = 2.24, gy = 2.16, and gz = 2.09, and a hyperfine constant of Az = 450 G. DFT calculations from crystal structure data reveal a J(Cu-Cl2aCu) of +3.6 at 296 K and +4.1 cm-1 at 90 K that dominates the magnetic properties, whereas J'(ππ) = 0.04 cm-1 is negligibly small.

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