Observation of TLIESST above Liquid Nitrogen Temperature and Disclosure of Hidden Hysteresis in Multiresponsive Hofmann-type Coordination Polymers.

Photoresponsive spin-crossover (SCO) molecules are an important class of bistable magnetic molecules with intriguing potential in device applications. The light-induced excited spin state trapping (LIESST) and the combined application of light and temperature can provide access to the metastable region of the SCO profile. The primary obstacle in utilizing light stimuli is the manifestation of light-induced trappings at extremely low temperatures. Herein, we report two novel multiresponsive 2D Hofmann-type coordination polymers exhibiting light-induced excited spin state trapping above liquid nitrogen temperature (TLIESST = 82 and 81 K). Stimulating the samples in conjugation with light and temperature successfully unveils hysteresis, which is otherwise concealed. Apart from light and temperature, we found that the SCO phenomenon is also responsive to external hydrostatic pressure and exhibits modulation of the hysteresis width and transition temperature shifts with changes in pressure.

Water-Stable, Eight-electron Acceptor Drives Anion∙∙∙Water Assisted Tunable Ionic Self-Assembly and Proton Conduction.

Organic π-scaffolds are being envisaged for new-age electron- and ion-responsive materials that can accumulate electrons as well as transport proton. However, such systems are extremely rare as electron-deficient scaffolds are unstable in aqueous solution. Here we detail the synthesis of a water-stable core-naphthalenediimide-nitrobenzyl-viologen based tetra-cation, which accumulates up to eight-electrons within an exceptionally narrow potential window of +0.05 V and -1.12 V. The supramolecular interactions and the ensuing ionic framework are tunable based on the three anions, e.g., Cl-, Br- and PF6-, that are investigated in this work. The ionic framework is formed and supported by a range of H-bonds, in which, the nitro benzyl groups act as pillars connecting the 1D water-tapes and the halide anions. The water molecules are hydrogen-bonded with the halide anions and bestow a facile pathway for the proton conduction, with proton conductivity up to 3.19 x 10-3 S cm-1. In contrast, the ionic assembly formed by the lipophilic PF6- anions do not host the water tapes and consequently the proton conductivity is found to be four orders of magnitude lower. This is a unique example, whereby proton conductivity is realized and is tunable within a highly electron-deficient, eight-electron acceptor, water-stable ionic supramolecular system.

Thermal and protonation-induced electron transfer coupled spin transition in a discrete [Fe2Co3] Prussian blue analogue.

Multi-stimuli responsive switchable molecules have garnered interest for their potential applications in the field of magnetic materials. However, the persistent challenge lies in isolating these properties within the same material. Herein, we report a discrete [Fe2Co3] pentanuclear cyanide bridged complex, [Co(L)2]3[Fe(CN)6]2·20H2O, (1) (L = (Z)-N'-(4-(trifluoromethyl)phenyl)picolinimidamide) which undergoes electron transfer coupled spin transition (ETCST) from [FeII2CoIIHSCoIII2] to [FeIII2CoII3] configurations through thermal activation and upon protonation.

Exploring the Magnetic Interactions in Two Novel Cyanide-Bridged Homo- and Heterometallic Hexadecanuclear Complexes.

Two novel isostructural cyanide-bridged hexadecanuclear complexes with the general formula {[Fe(CN)6]6[M{en(Bn)py}]10}2+ [M=Fe (12+), Ni (22+)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 12+ whereas all the Fe centres share a conserved oxidation state in complex 22+. The DC magnetic study revealed antiferromagnetic interactions between the adjacent metal centres and ferrimagnetic behaviour in 12+. On the other hand, ferromagnetic interactions were observed in complex 22+ due to nearly orthogonal orientation of the interacting orbitals and poor spatial overlap as observed in BS-DFT calculations.

Unraveling Multicopper [Cu3] and [Cu6] Clusters with Rare µ3-Sulfato and Linear µ2-Oxido-Bridges as Potent Antibiofilm Agents against Multidrug-Resistant Staphylococcus aureus.

In this research article, two multicopper [Cu3] and [Cu6] clusters, [Cu3(cpdp)(µ3-SO4)(Cl)(H2O)2]·3H2O (1) and [Cu6(cpdp)2(µ2-O)(Cl)2(H2O)4]·2Cl (2) (H3cpdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol), have been explored as potent antibacterial and antibiofilm agents. Their molecular structures have been determined by a single-crystal X-ray diffraction study, and the compositions have been established by thermal and elemental analyses, including electrospray ionization mass spectrometry. Structural analysis shows that the metallic core of 1 is composed of a trinuclear [Cu3] assembly encapsulating a µ3-SO42- group, whereas the structure of 2 represents a hexanuclear [Cu6] assembly in which two trinuclear [Cu3] motifs are exclusively bridged by a linear µ2-O2- group. The most striking feature of the structure of 2 is the occurrence of an unusual linear oxido-bridge, with the Cu3-O6-Cu3' bridging angle being 180.00°. Whereas 1 can be viewed as an example of a copper(II)-based compound displaying a rare µ3:η1:η1:η1 bridging mode of the SO42- group, 2 is the first example of any copper(II)-based compound showing an unsupported linear Cu-O-Cu oxido-bridge. Employing variable-temperature SQUID magnetometry, the magnetic susceptibility data were measured and analyzed exemplarily for 1 in the temperature range of 2-300 K, revealing the occurrence of antiferromagnetic interactions among the paramagnetic copper centers. Both 1 and 2 exhibited potent antibacterial and antibiofilm activities against methicillin-resistant Staphylococcus aureus (MRSA BAA1717) and the clinically isolated culture of methicillin-resistant S. aureus (MRSA CI1). The mechanism of antibacterial and antibiofilm activities of these multicopper clusters was investigated by analyzing and determining the intracellular reactive oxygen species (ROS) generation, lipid peroxidation, microscopic observation of cell membrane disruption, membrane potential, and leakage of cellular components. Additionally, 1 and 2 showed a synergistic effect with commercially available antibiotics such as vancomycin with enhanced antibacterial activity. However, 1 possesses higher antibacterial, antibiofilm, and antivirulence actions, making it a potent therapeutic agent against both MRSA BAA1717 and MRSA CI1 strains.

Single-Molecule Magnet Behavior of Confined Dy(III) in a Mixed Heteroatom-Substituted Polyoxotungstate.

Two heteroatom-templated Dy(III)-confined polyoxotungstates [H2N(CH3)2]7Na7[Dy2(H2O)7(W4O9)(HPSeW15O54)(α-SeW9O33)2]·31H2O (1) and [H2N(CH3)2]14K2Na18{[Dy2(H2O)13W14O40]2[α-SeW9O33]4[HPSeW15O54]2}·44H2O (2) were synthesized by a one-pot aqueous reaction and structurally characterized. The most distinctive structural feature of complexes 1 & 2 is the simultaneous presence of both trivacant Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building blocks containing P(III)-Se(IV) heteroatoms. The trimeric polyanion of 1 can be represented as a fusion of two trivacant Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building units encapsulating the [Dy2(H2O)7(W4O9)]12+ cluster. On the other hand, hexameric polyoxoanions of 2 are described as four trivacant Keggin [α-SeW9O33]8- and two Dawson [HPSeW15O54]10-, building units anchoring a [Dy4(H2O)26W28O80]20+ cluster. The magnetic investigation revealed the presence of significant magnetic anisotropy and slow relaxation of magnetization behavior for complex 1 with a phenomenological energy barrier, Ueff = 13.58 K in the absence of an external magnetic field, and Ueff = 24.57 K in the presence of a 500 Oe external dc magnetic field. On the other hand, complex 2 favors the QTM relaxation process in the absence of an external magnetic field and shows field-induced slow relaxation of magnetization with Ueff = 11.11 K at 1500 Oe applied dc field. The in-depth analysis of magnetic relaxation dynamics shows that the relaxation process follows the Orbach as well as Raman relaxation pathways. Further, the ab initio calculation of the studied complexes confirms that the highly axial ground and first excited energy states (containing pure highest mJ states) are responsible for the observed single-molecule magnet (SMM) behavior. Remarkably, this is the first example of a mixed heteroatom-based Dy(III)-substituted polyoxotungstate with both trimeric Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building units showing SMM behavior.

Modulation of single-chain magnet behaviour in a heterometallic Fe2Co cyanide-bridged 2D sheet.

A cyanide-bridged Fe2Co 2D sheet exhibiting electron transfer coupled spin transition (ETCST) with co-existence of magnetic ordering below 50 K is reported. The complex exhibits single-chain magnet behaviour where the uncoordinated water molecules act as an exchange-breaking impurity by allowing only a fraction of the molecule to undergo a spin state change. The paramagnetic centres prevail throughout the chain on desolvation, thereby increasing the number of correlated units in the chain.

[α-AsW9O33]9- bridged hexagonal clusters of Ln(III) showing field induced SMM behavior: experimental and theoretical insight.

Polyoxometalates (POM), as inorganic polydentate oxygen donors, provide binding opportunities for oxophilic lanthanide metal centers to construct novel Ln-substituted POM materials with exciting structures and attractive properties. Herein, we have reported four arsenotungstate [α-AsW9O33]9- based lanthanide-containing polyoxometalates [CsxK36-x{Ln6(H2O)12(α-AsW9O33)6}]·yH2O (Ln = Er (1), Gd (2), Ho (3), and Tb (4)), which are synthesized in an alkaline medium. Complexes 1-3 are the dimeric structures of [Ln3(H2O)6(α-AsW9O33)3]18- polyanions, whereas complex 4 is a hexamer of the polyanion [Tb (H2O)2(α-AsW9O33)]6- as a building unit. In all the complexes, [α-AsW9O33]9- units are staggered up and down and give rise to the chair conformation, where one [α-AsW9O33]9- unit bridges two Ln(III) centers through four µ2-oxygen and two terminal oxygen atoms, resulting in the hexagonal arrangement of lanthanides. The dynamic magnetic measurement indicates that only complex 1 exhibits slow relaxation of magnetization with an applied dc field (1500 Oe). To gain insight into the slow relaxation of magnetization in complex 1, the ligand-field parameters and the splitting of the ground-state multiplet of the Er(III) ions have been estimated. The ab initio calculation results confirm that the ground state wave function of these molecules (1, 3, and 4) is mainly composed of a mixture of mJ states, and the non-axial crystal field (CF) terms are more predominant than the axial CF term. The solid-state fluorescence spectra of 1-4 reveal that the photoexcitation O → M ligand-to-metal charge-transfer (LMCT) of arsenotungstate fragments is effectively quenched due to the spatial coordination environment around the Ln(III) ion.

Dinuclear Iron(II) Triple Helicates Exhibiting Room Temperature Spin-Transition Behaviour in Solid and Solution Phase.

Herein, three dinuclear iron(II) helicates bearing the molecular formula [Fe2 (L1)3 ](ClO4 )4 ⋅ 2CH3 OH ⋅ 3H2 O (complex 1), [Fe2 (L2)3 ](ClO4 )4 ⋅ 6CH3 CN (complex 2), and [Fe2 (L3)3 ](ClO4 )4 ⋅ 0.5H2 O (complex 3) have been synthesized using imidazole and pyridine-imine-based ligands having fluorene moiety in the backbone. A change in the ligand field strength by terminal modulation led to a change in the spin-transition behaviour from incomplete, multi-step to complete, around room temperature in the solid state. Spin transition behaviour has also been observed in the solution phase characterized using variable temperature 1 H nuclear magnetic resonance spectroscopy (Evans method) and correlated using UV-visible spectroscopy. Fitting the NMR data using the ideal solution model yielded the transition temperature in the order T1/2 (1)

Significant Control on Zero-Field Quantum Tunneling of Magnetization in Dysprosium Based Single-Molecule Magnets via Orientation of the Anilato Ligand.

Tuning the bridging fashion of anilato ligand in dinuclear DyIII complexes, reveals a sizable effect on the slow relaxation of magnetization. Combined experimental and theoretical studies divulge that the geometry with high order axial symmetry (pseudo square antiprism) reduces the transverse crystal fields corresponding to QTM (quantum tunneling of magnetization) resulting in a significant increase in energy barrier (Ueff =518 cm-1 ) through the Orbach relaxation process whereas the geometry with lower symmetry (triangular dodecahedron, pseudo D2d ) enhances the transverse crystal fields that accelerate the ground state QTM process. Notably, the value 518 cm-1 represents the highest energy barrier among anilato ligand based SMMs.

NaGaSe2: A Water-Loving Multifunctional Non-van der Waals Layered Selenogallate.

A missing member of well-known ternary chalcometallates, a sodium selenogallate, NaGaSe2, has been synthesized by employing a polyselenide flux and stoichiometric reaction. Crystal structure analysis using X-ray diffraction techniques reveals that it contains supertetrahedral adamantane-type Ga4Se10 secondary building units. These Ga4Se10 secondary building units are further connected via corners to form two-dimensional (2D) [GaSe2]∞- layers stacked along the c-axis of the unit cell, and the Na ions reside in the interlayer space. The compound has an unusual ability to absorb water molecules from the atmosphere or a nonanhydrous solvent to form distinct hydrated phases, NaGaSe2·xH2O (where x can be 1 and 2), with an expanded interlayer space, as verified by X-ray diffraction (XRD), thermogravimetric-differential scanning calorimetry (TG-DSC), desorption, and Fourier transform infrared spectroscopy (FT-IR) studies. The in situ thermodiffractogram indicates the emergence of an anhydrous phase before 300 °C with the decrease of interlayer spacings and reverting to the hydrated phase within a minute of re-exposure to the environment, supporting the reversibility of such a process. Structural transformation induced through water absorption results in an increase of Na ionic conductivity by 2 orders of magnitude compared to that of the pristine anhydrous phase, as verified by impedance spectroscopy. Na ions from NaGaSe2 can be exchanged in the solid-state route with other alkali and alkaline earth metals in a topotactic or nontopotactic way, leading to 2D isostructural and three-dimensional networks, respectively. Optical band gap measurements show a band gap of ∼3 eV for the hydrated phase, NaGaSe2·xH2O, which is in good agreement with the calculated band gap using a density functional theory (DFT)-based method. Sorption studies further confirm the selective absorption of water over MeOH, EtOH, and CH3CN with a maximum water uptake of 6 molecules/formula unit at a relative pressure, P/P0, of 0.9.

Windmill-like Ln4 Clusters [Ln = Tb(III) and Dy(III)] Bridged by [α-AsW9O33]9- Unit Showing Zero-Field SMM Behavior: Experimental and Theoretical Investigation.

Herein, two polyoxometalate (POM)-ligated tetranuclear rare-earth metal complexes having the molecular formula [CsxK24-x{Ln4(H2O)8(α-AsW9O33)4}]·yH2O {x = 5, y = 20, and Ln = Tb(III) (1); and x = 6, y = 28, and Ln = Dy(III) (2)} were synthesized by a one-pot reaction with LnCl3·6H2O using di-lacunary [As2W19O67(H2O)]14- precursor and characterized. The structural analysis shows that the building units [α-AsW9O33]9- are bridged by four rare-earth ions, where one [α-AsW9O33]9- bridged two Ln(III) centers asymmetrically by µ2-O and terminal oxygen atoms. The [α-AsW9O33]9- units are orthogonal to each other, resembling as vanes of a windmill. The magnetic studies disclosed the presence of large magnetic anisotropy and slow relaxation of magnetization behavior [Ueff = 15.2 K (1) and 26 K (2)] in the absence of an external magnetic field. Detailed analysis of relaxation dynamics confirmed that the QTM process in 2 (τQTM = 2.50 × 10-4 s) is slower as compared to complex 1 (τQTM = 2.38 × 10-4 s), and the relaxation process mainly follows the shortcut pathways (such as QTM, optical, and acoustic phonon process) rather than the thermally activated Orbach process. Further, the ab initio calculations show high axial ground states with minimum transverse anisotropy and provide a good agreement between calculated and experimental magnetic data for both complexes. It has also been observed that the local symmetry (D4d subgroup) around the metal centers in 1 provides higher axiality and stabilizes mJ = ±6 of Tb(III) more as compared to mJ = ±15/2 of Dy (III) in 2, resulting in higher energy splitting of the ground state in the former complex. The combined experimental and theoretical observations suggest that the high axial nature of the ground state with minimum transverse anisotropy resulting from local ligand field symmetry is responsible for the observed zero-field single-molecule magnet (SMM) behavior in the studied complexes. Notably, complex 1 is the first example of a POM-based terbium complex that shows SMM behavior in the absence of an external field.

Effect of intermolecular anionic interactions on spin crossover of two triple-stranded dinuclear Fe(II) complexes showing above room temperature spin transition.

Two new Fe(II)-based dinuclear triple helicates having the formula {[Fe2(L)3]·(CF3SO3)4·6.5H2O·CH3OH} (complex 1) and {[Fe2(L)3]·(ClO4)4·7H2O·1.35CH3OH} (complex 2), displaying near room temperature spin transition have been synthesized and the effect of intermolecular interactions and co-operativity between metal centers on the spin crossover (SCO) has been studied. Picolinimidamide-based ligand system is chosen to provide maximum intermolecular interactions. Variable-temperature single crystal X-ray diffraction (SCXRD), magnetic study, and Hirshfeld analysis reveal that complex 1 shows a multistep spin transition, whereas, complex 2 shows an abrupt spin transition from [LS-LS] ↔ [HS-HS]. In complex 2 the presence of perchlorate anion induces high intermolecular O-H interaction that enhances the cooperativity resulting in high T1/2 of 330 K. This study accentuates the interplay between anion effect, crystal packing, and supramolecular interactions in tuning the magnetic properties of SCO compounds.

Spin-State Modulation in FeII -Based Hofmann-Type Coordination Polymers: From Molecules to Materials.

Spin crossover complexes that reversibly interconvert between two stable states imitate a binary state of 0 and 1, delivering a promising possibility to address the data processing concept in smart materials. Thus, a comprehensive understanding of the modulation of magnetic transition between high spin and low spin and the factors responsible for stabilizing the spin states is an essential theme in modern materials design. In this context, the present review attempts to provide a concise outline of the design strategy employed at the molecular level for fine-tuning the spin-state switching in FeII -based Hofmann-type coordination polymers and their effects on the optical and magnetic response. In addition, development towards the nanoscale architectures of HCPs, i. e., in terms of nanoparticles and thin films, are emphasized to bridge the gap between the laboratory and reality.

Multifunctional Lanthanide-Doped Binary Fluorides and Graphene Oxide Nanocomposites Via a Task-Specific Ionic Liquid.

Graphene oxide-based nanocomposites (NCMs) exhibit diverse photonic and biophotonic applications. Innovative nanoengineering using a task-specific ionic liquid (IL), namely, 1-butyl-3-methyl tetrafluoroborate [C4mim][BF4], allows one to access a unique class of luminescent nanocomposites formed between lanthanide-doped binary fluorides and graphene oxide (GO). Here the IL is used as a solvent, templating agent, and as a reaction partner for the nanocomposite synthesis, that is, "all three in one". Our study shows that GO controls the size of the NCMs; however, it can tune the luminescence properties too. For example, the excitation spectrum of Ce3+ is higher-energy shifted when GO is attached. In addition, magnetic properties of GdF3:Tb3+ nanoparticles (NPs) and GdF3:Tb3+-GO NCMs are also studied at room temperature (300 K) and very low temperature (2 K). High magnetization results for the NPs (e.g., 6.676 emu g-1 at 300 K and 184.449 emu g-1 at 2 K in the applied magnetic field from +50 to -50 kOe) and NCMs promises their uses in many photonic and biphotonic applications including magnetic resonance imaging, etc.

Heterometallic Hexanuclear [Cu2 Ln4 ] Complexes Showing Zero-field SMM Behaviour and Magnetocaloric Effect.

Three heterometallic hexanuclear 3d-4f complexes bearing the formula [Cu2 (L)2 Ln4 (L)4 (o-van)2 ] [L=2-((E)-((2-hydroxyphenyl)imino]methyl)phenol; o-van=ortho-vanillin] (LnIII =GdIII (1), DyIII (2), and TbIII (3)) have been synthesized and characterized. DC magnetic susceptibility measurements reveal overall antiferromagnetic interactions in 1 and 3, whereas co-existence of ferro- as well as antiferromagnetic interactions were observed in 2. The magnetocaloric effect has been observed for 1 with an entropy change (-ΔSm ) of 22.3 J kg-1 K-1 at 3 K and 7 T. Zero-field single molecule magnet (SMM) behaviour has been observed for 2, where Raman relaxation and quantum tunneling of magnetization (QTM) played a role in magnetization relaxation. The Cu-O-Ln angle well explains the magnetic exchange coupling occurring in the complexes. BS-DFT calculation for the complexes provides an estimate of the exchange interactions between the paramagnetic centres. Ab initio calculations performed for complex 2 established a good correlation to the experimental relaxation dynamics.

Reversible redox switching between local and global aromaticity for core-modified expanded carbaisophlorinoids.

Two dithienothiophene based 28π antiaromatic macrocycles with benzene and azulene units and their effects on local and global (anti)aromaticity have been described. Experimental and computational studies confirmed the presence of weak paratropic and strong diatropic ring current effects in neutral and dicationic states, respectively.

A tetra Co(II/III) complex with an open cubane Co4O4 core and square-pyramidal Co(II) and octahedral Co(III) centres: bifunctional electrocatalytic activity towards water splitting at neutral pH.

The reaction of 2,6-diformyl-4-methylphenol, 4-methoxybenzoylhydrazine and Co(OAc)2·4H2O in 1 : 2 : 2 mole ratio in methanol under aerobic conditions produced in 61% yield a tetranuclear complex having the molecular formula [CoIICoIII(µ-OAc)(µ3-OH)(µ-L)]2 where OAc- and L3- represent acetate and N',N''-(5-methyl-2-oxido-1,3-phenylene)bis(methan-1-yl-1-ylidene)bis(4-methoxybenzoylhydrazonate), respectively. The elemental analysis and the mass spectrometric data confirmed the molecular formula of the complex. It is electrically non-conducting and paramagnetic. The complex crystallized as acetonitrile solvate. The X-ray structure shows that each Co(II) centre has a distorted square-pyramidal NO4 coordination sphere, while each Co(III) centre is in a distorted octahedral NO5 environment. The four metal atoms and the four bridging O-atoms form an open cubane type Co4O4 motif. In the crystal lattice, self-assembly of the solvated complex via intermolecular O-H⋯O interaction leads to a two-dimensional network structure. The infrared and electronic spectroscopic features of the complex are consistent with its molecular structure. Cryomagnetic measurements together with theoretical calculations suggest the presence of easy-axis anisotropy for the square-pyramidal Co(II) centres. The complex is redox-active and displays metal centred oxidation and reduction responses on the anodic and cathodic sides, respectively, of the Ag/AgCl electrode. Bifunctional heterogeneous electrocatalytic activity of the complex towards O2 and H2 evolution reactions (OER and HER) in neutral aqueous medium has been explored in detail.

Co3Gd4 Cage as Magnetic Refrigerant and Co3Dy3 Cage Showing Slow Relaxation of Magnetisation.

Two structurally dissimilar 3d-4f cages having the formulae [(CoIII)3Gd4(µ3-OH)2(CO3) (O2CtBu)11(teaH)3]·5H2O (1) and [(CoIII)3Dy3(µ3-OH)4(O2CtBu)6(teaH)3]·(NO3)2·H2O (2) have been isolated under similar reaction conditions and stoichiometry of the reactants. The most important factor for structural diversity seems to be the incorporation of one µ3-carbonate anion in 1 and not in 2. Co atoms are in a +3 oxidation state in both complexes, as shown by the Bond Valence Sum (BVS) calculations and bond lengths, and as further supported by magnetic measurements. Co3Gd4 displays a significant magnetocaloric effect (-∆Sm = 25.67 J kg-1 K-1), and Co3Dy3 shows a single molecule magnet (SMM) behavior.

Effect of an axial coordination environment on quantum tunnelling of magnetization for dysprosium single-ion magnets with theoretical insight.

Herein, we report two mononuclear dysprosium complexes [Dy(H4L){B(OMe)2(Ph)2}2](Cl)·MeOH (1) and [Dy(H4L){MeOH)2(NCS)2}](Cl) (2) [where H4L = 2,2'-(pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(N-phenylhydrazinecarboxamide)] with different axial coordination environments. The structural analysis revealed that the pentadentate H4L ligand binds through the equatorial position in both complexes. In complex 1, the axial positions are occupied by bidentate dimethoxydiphenyleborate [B(OMe)2(Ph)2]-. On the other hand, in complex 2, one axial position is occupied by two NCS- and one MeOH molecule while another MeOH molecule is coordinated to the other axial position. Magnetic measurements disclose the presence of field-induced slow relaxation of magnetization with an energy barrier of Ueff = 30 K for 1 whereas no such effective barrier was observed in complex 2. Detailed analysis of field and temperature dependence of the relaxation time confirms the major role of Raman, QTM, and direct processes rather than the Orbach process in complex 1. It was observed that [B(OMe)2(Ph)2]- provides higher axial anisotropy which slows down the QTM process (relaxation time for the QTM process is 2.70 × 10-5 s) in 1 as compared to NCS anions and MeOH molecules in 2 (1.03 × 10-8 s), and is responsible for the absence of an effective energy barrier in the latter complex as confirmed by ab initio calculations. The calculations also show that the presence of a large bidentate dimethoxydiphenyleborate ligand in axial positions may result in high-performance Dy-based single-ion magnets.