Motional Narrowing Effects in the Excited State Spin Populations of Mn-Doped Hybrid Perovskites.

Spin-orbit coupling in the electronic states of solution-processed hybrid metal halide perovskites forms complex spin-textures in the band structures and allows for optical manipulation of the excited state spin-polarizations. Here, we report that motional narrowing acts on the photoexcited spin-polarization in CH3NH3PbBr3 thin films, which are doped at percentage-level with Mn2+ ions. Using ultrafast circularly polarized broadband transient absorption spectroscopy at cryogenic temperatures, we investigate the spin population dynamics in these doped hybrid perovskites and find that spin relaxation lifetimes are increased by a factor of 3 compared to those of undoped materials. Using quantitative analysis of the photoexcitation cooling processes, we reveal increased carrier scattering rates in the doped perovskites as the fundamental mechanism driving spin-polarization-maintaining motional narrowing. Our work reports transition-metal doping as a concept to extend spin lifetimes of hybrid perovskites.

Probing the Origin of Ferro-/Antiferromagnetic Exchange Interactions in Cu(II)-4f Complexes.

The mechanistic investigations between Cu(II) and the anisotropic lanthanides (Ln(III)) are not much explored to date. This is due to the complicated energy spectrum which arises due to the orbital angular momentum of anisotropic lanthanides. Interestingly, the exchange coupling J in Ln(III)-Cu(II) systems was found to be antiferromagnetic for <4f7 metal ions and ferromagnetic for ≥4f7 metal ions, while the net magnitude of JTotal strength gradually decreases moving from f1 to f13. While this is established in several examples, the reason for this intriguing trend is not rationalized. In this article, we have taken up these challenging tasks by synthesizing a family of complexes with the general molecular formula [Cu2Ln(HL)4(NO3)](NO3)2, where Ln = La (1-La), Ce (2-Ce), Pr (3-Pr), Gd (4-Gd), Tb (5-Tb), Dy (6-Dy), and Ho (7-Ho) and HL = C15H15N1O3; (2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate) is a monodeprotonated tridentate Schiff base ligand. Detailed dc magnetic susceptibility measurements performed for all the complexes reveal that the Cu(II) ion is coupled ferromagnetically to the respective Ln(III) ion, which has more than seven electrons in the 4f shell, while an antiferromagnetic coupling is witnessed if Ln(III) has less than seven electrons. The strength of the exchange coupling constant was quantitatively determined for representative complexes from the high-field/high-frequency electron paramagnetic resonance spectroscopy which follows the order of 4-Gd (1.50(10) cm-1) > 5-Tb (1.18(10) cm-1) > 6-Dy (0.56(10) cm-1 based on the -2JCu-Ln(SCu1→·JLnz→+SCu2→·JLnz→) spin Hamiltonian. The increased axiality in 5-Tb and 6-Dy due to the presence of 3d ions in the near vicinity of an oblate ion and the increased exchange coupling strength between Cu(II) and Tb(III) or Dy(III) is the ideal combination to stabilize magnetic bistability in these complexes in the absence of an external magnetic field with the effective energy barrier of 15.7 K (τo = 2.49 × 10-6 s) and 12.6 K (τo = 1.70 × 10-5 s), respectively. To rationalize this experimental trend, we have performed ab initio CASSCF and DFT calculations. To compute the J values, we have employed POLY_ANISO routines and utilized the computed data to establish the generic mechanism of magnetic coupling in {Cu-Ln-Cu} motifs. These mechanistic findings reveal the importance of 5d orbitals and their energy with respect to the dx2-y2 orbital of Cu(II) ions in controlling the magnetic coupling of {Cu-4f} complexes.

Role of Coordination Geometry on the Magnetic Relaxation Dynamics of Isomeric Five-Coordinate Low-Spin Co(II) Complexes.

To investigate the influence of the coordination geometry on the magnetization relaxation dynamics, two geometric isomers of a five-coordinate low-spin Co(II) complex with the general molecular formula [Co(DPPE)2Cl]SnCl3 (DPPE = diphenylphosphinoethane) were synthesized and structurally characterized. While one isomer has a square pyramidal geometry (Co-SP (1)), the other isomer figures a trigonal bipyramidal geometry (Co-TBP (2)). Both complexes were already reported elsewhere. The spin state of these complexes is unambiguously determined by detailed direct current (dc) magnetic data, X-band, and high-frequency EPR measurements. Slow relaxation of magnetization is commonly observed for systems with S > 1/2. However, both 1 and 2 show field-induced slow relaxation of magnetization. Especially 1 shows relaxation times up to τ = 35 ms at T = 1.8 K, which is much longer than the reported values for undiluted Co(II) low-spin monomers. In 2, the maximal field-induced relaxation time is suppressed to τ = 5 ms. We attribute this to the change in g-anisotropy, which is, in turn, correlated to the spatial arrangement of ligands (i.e., coordination geometry) around the Co(II) ions. Besides the detailed electronic structure of these complexes, the experimental observations are further corroborated by theoretical calculations.

Magnetic behavior of the novel pentagonal-bipyramidal erbium(III) complex (Et3NH)[Er(H2DAPS)Cl2]: high-frequency EPR study and crystal-field analysis.

We report the synthesis, crystal structure and magnetic properties of the new heptacoordinated mononuclear erbium(III) complex (Et3NH)[Er(H2DAPS)Cl2] (H4DAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) (1). The coordination polyhedron around the Er(III) ion features a slightly distorted pentagonal bipyramid formed by the pentagonal N3O2 chelate ring of the H2DAPS ligand in the equatorial plane and two apical chloride ligands. Detailed high-frequency/high-field electron paramagnetic resonance (HF-EPR) studies of 1 result in the precise determination of the crystal field (CF) splitting energies (0, 290 and 460 GHz) and effective g-values of the three lowest Kramers doublets (KDs) of the Er(III) ion. The obtained HF-EPR data are in good agreement with the results from CF analysis for the Er(III) ion based on the simulation of the dc magnetic data of 1. The results from dynamic susceptibility measurements indicate that there is no slow relaxation of magnetisation behaviour. This observation is discussed in terms of the electronic structure of 1 obtained from experimental and theoretical results.

Validation of Ab-Initio-Predicted Magnetic Anisotropies and Magneto-structural Correlations in Linear Hetero-trinuclear DyIII -NiII 2 Compounds.

Reported are single crystal SQUID and single crystal high-frequency/high-field EPR data of a trinuclear complex with a rare six-coordinate coordination sphere of a DyIII center coupled to two terminal six-coordinate NiII ions. The analysis of the single crystal spectroscopic parameters allows for an accurate description of the ground state wavefunction. The experimental analysis is supplemented by the analysis of the paramagnetic NMR spectra, allowing for a thorough description of the DyIII center. The experimental data are interpreted on the basis of an ab initio ligand field analysis, and the computed parameters are in good agreement with the experimental observations. This supports the quality of the theoretical approach based on a pseudo-spin Hamiltonian for the electronic ground state. Further support emerges from the ab initio ligand field theory based analysis of a structurally very similar system that, in contrast to the complex reported here, shows single molecule magnetic properties, and this is in agreement with the quantum-chemical prediction and analysis.

The first pentagonal-bipyramidal vanadium(III) complexes with a Schiff-base N3O2 pentadentate ligand: synthesis, structure and magnetic properties.

A series of three mononuclear pentagonal-bipyramidal V(iii) complexes with the equatorial pentadentate N3O2 ligand (2,6-diacethylpyridinebis(benzoylhydrazone), H2DAPBH) in the different charge states (H2DAPBH0, HDAPBH1-, DAPBH2-) and various apical ligands (Cl-, CH3OH, SCN-) were synthesized and characterized structurally and magnetically: [V(H2DAPBH)Cl2]Cl·C2H5OH (1), [V(HDAPBH)(NCS)2]·0.5CH3CN·0.5CH3OH (2) and [V(DAPBH)(CH3OH)2]Cl·CH3OH (3). All three complexes reveal paramagnetic behavior, resulting from isolated S = 1 spins with positive zero-field splitting energy expected for the high-spin ground state of the V3+ (3d2) ion in a PBP coordination. Detailed high-field EPR measurements for compound 3 show that its magnetic properties are best described by using the spin Hamiltonian with the positive ZFS energy (D = +4.1 cm-1) and pronounced dimer-like antiferromagnetic spin coupling (J = -1.1 cm-1). Theoretical analysis based on superexchange calculations reveals that the long-range spin coupling between distant V3+ ions (8.65 Å) is mediated through π-stacking contacts between the planar DAPBH2- ligands of two neighboring [V(DAPBH)(CH3OH)2]+ complexes.

Filled Carbon Nanotubes as Anode Materials for Lithium-Ion Batteries.

Downsizing well-established materials to the nanoscale is a key route to novel functionalities, in particular if different functionalities are merged in hybrid nanomaterials. Hybrid carbon-based hierarchical nanostructures are particularly promising for electrochemical energy storage since they combine benefits of nanosize effects, enhanced electrical conductivity and integrity of bulk materials. We show that endohedral multiwalled carbon nanotubes (CNT) encapsulating high-capacity (here: conversion and alloying) electrode materials have a high potential for use in anode materials for lithium-ion batteries (LIB). There are two essential characteristics of filled CNT relevant for application in electrochemical energy storage: (1) rigid hollow cavities of the CNT provide upper limits for nanoparticles in their inner cavities which are both separated from the fillings of other CNT and protected against degradation. In particular, the CNT shells resist strong volume changes of encapsulates in response to electrochemical cycling, which in conventional conversion and alloying materials hinders application in energy storage devices. (2) Carbon mantles ensure electrical contact to the active material as they are unaffected by potential cracks of the encapsulate and form a stable conductive network in the electrode compound. Our studies confirm that encapsulates are electrochemically active and can achieve full theoretical reversible capacity. The results imply that encapsulating nanostructures inside CNT can provide a route to new high-performance nanocomposite anode materials for LIB.

Influence of a Counteranion on the Zero-Field Splitting of Tetrahedral Cobalt(II) Thiourea Complexes.

Four mononuclear cobalt(II) complexes with pseudo tetrahedral geometry were isolated with different counteranions; their structure solution reveals the molecular formula as [Co(L1)4]X2 [where L1 = thiourea (NH2CSNH2) and X = NO3 (1), Br (2), and I (3)] and [Co(L1)4](SiF6) (4). The detailed analysis of direct-current (dc) magnetic data reveals a zero-field splitting (ZFS; D) with mS = ±3/2 as the ground levels (D < 0) for the four complexes. The magnitude of the ZFS parameter is larger, in absolute value, for 1 (D = -61.7 cm-1) than the other three complexes (-5.4, -5.1, and -12.2 cm-1 for 2-4, respectively). The sign of D for 1, 2, and 4 was unambiguously determined by X-band electron paramagnetic resonance (EPR) spectroscopy of the diluted samples (10%) at 5 K. For 3, the sign of D was naturally endorsed from the frequency-dependent out-of-phase signal (χM″) observed in the absence of an external dc magnetic field and confirmed by high-frequency EPR (70-600 GHz) experiments performed on a representative pure polycrystalline 3, which gave a quantitative D value of -5.10(7) cm-1. Further, the drastic changes in the spin Hamiltonian parameters and their related relaxation dynamics phenomena (of 2-4 compared to 1) were rationalized using ab initio complete-active-space self-consistent field/n-electron valence perturbation theory calculations. Calculations disclose that the anion-induced structural distortion observed in 2-4 leads to a nonfavorable overlap between the π orbital of cobalt(II) and the π* orbital of the sulfur atom that reduces the overall |D| value in these complexes compared to 1. The present study demonstrates that not only the first but also the second coordination sphere significantly influences the magnitude of the ZFS parameters. Particularly, a reduction of D of up to ∼90% occurs (in 2-4 compared to 1) upon a simple variation of the counteranions and offers a viable approach to modulate ZFS in transition-metal-containing single-molecule magnets.

From polystyrene waste to porous carbon flake and potential application in supercapacitor.

Due to white pollution related environmental concern and sustainable development requirement, it is desirable to recycle the widely used plastic wastes into products with commercial value, such as high-valued carbon materials which can be applied in electrochemical fields. In this work, porous carbon flakes (PCFs) are produced by direct pyrolysis of polystyrene waste through template method. Furthermore, manganese dioxide (MnO2) nanosheets are selectively deposited on the surface of resultant PCFs to form hybrid (PCF-MnO2). Because of the large specific surface area (1087 m2/g) and high conductivity of PCFs, native high specific capacity of MnO2, and positive synergistic interaction between PCF and MnO2, the resulting hybrid materials show an ultrahigh capacitance of 308 F/g at 1 mV/s and 247 F/g at 1 A/g in LiCl electrolyte, and excellent cycle stability of 93.4% capacitance retention over 10,000 cycles at 10 A/g in symmetric supercapacitor device. This work demonstrates a convenient method for the preparation of cost-effective and high-performance electrode material for electric capacitor. More importantly, it provides a potential way to recycle polystyrene waste into high-valued product in large-scale with disposing of polymeric waste to alleviate environmental concerns.

Single-crystalline FeCo nanoparticle-filled carbon nanotubes: synthesis, structural characterization and magnetic properties.

In the present work, we demonstrate different synthesis procedures for filling carbon nanotubes (CNTs) with equimolar binary nanoparticles of the type Fe-Co. The CNTs act as templates for the encapsulation of magnetic nanoparticles and provide a protective shield against oxidation as well as prevent nanoparticle agglomeration. By variation of the reaction parameters, we were able to tailor the sample purity, degree of filling, the composition and size of the filling particles, and therefore, the magnetic properties. The samples were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), superconducting quantum interference device (SQUID) and thermogravimetric analysis (TGA). The Fe-Co-filled CNTs show significant enhancement in the coercive field as compared to the corresponding bulk material, which make them excellent candidates for several applications such as magnetic storage devices.

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes.

The electronic and magnetic properties of a set of mononuclear terbium(III) and dysprosium(III) complexes with two tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands are reported. Two primary coordination geometries are observed, depending on the length of the linker between the 1,2-HOPO donor moieties and the resulting arrangements of the linker. Fine details of the magnetic circular dichroism (MCD) spectra of the dysprosium(III) complexes illustrate differences in the splitting of the J multiplets and allow for a thorough ligand field analysis. High frequency electron paramagnetic resonance (HF-EPR) studies of the terbium(III) complexes give insight into the composition of the ground states. Ab initio calculations are utilized to rationalize the experimental results and further illustrate the effect of the structural features on the electronic and magnetic properties of the different complexes.

A2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties.

Four new manganese germanates and silicates, A2MnGeO4 (A = Li, Na) and A2MnSiO4 (A = Na, Ag), were prepared, and their crystal structures were determined using the X-ray Rietveld method. All of them contain all components in tetrahedral coordination. Li2MnGeO4 is orthorhombic (Pmn21) layered, isostructural with Li2CdGeO4, and the three other compounds are monoclinic (Pn) cristobalite-related frameworks. As in other stuffed cristobalites of various symmetry (Pn A2MXO4, Pna21 and Pbca AMO2), average bond angles on bridging oxygens (here, Mn-O-X) increase with increasing A/X and/or A/M radius ratios, indicating the trend to the ideal cubic (Fd3̅m) structure typified by CsAlO2. The sublattices of the magnetic Mn2+ ions in both structure types under study (Pmn21 and Pn) are essentially the same; namely, they are pseudocubic eutaxy with 12 nearest neighbors. The magnetic properties of the four new phases plus Li2MnSiO4 were characterized by carrying out magnetic susceptibility, specific heat, magnetization, and electron spin resonance measurements and also by performing energy-mapping analysis to evaluate their spin exchange constants. Ag2MnSiO4 remains paramagnetic down to 2 K, but A2MnXO4 (A = Li, Na; X = Si, Ge) undergo a three-dimensional antiferromagnetic ordering. All five phases exhibit short-range AFM ordering correlations, hence showing them to be low-dimensional magnets and a magnetic field induced spin-reorientation transition at T < TN for all AFM phases. We constructed the magnetic phase diagrams for A2MnXO4 (A = Li, Na; X = Si, Ge) on the basis of the thermodynamic data in magnetic fields up to 9 T. The magnetic properties of all five phases experimentally determined are well explained by their spin exchange constants evaluated by performing energy-mapping analysis.

Electrochemical Magnetization Switching and Energy Storage in Manganese Oxide filled Carbon Nanotubes.

The ferrimagnetic and high-capacity electrode material Mn3O4 is encapsulated inside multi-walled carbon nanotubes (CNT). We show that the rigid hollow cavities of the CNT enforce size-controlled nanoparticles which are electrochemically active inside the CNT. The ferrimagnetic Mn3O4 filling is switched by electrochemical conversion reaction to antiferromagnetic MnO. The conversion reaction is further exploited for electrochemical energy storage. Our studies confirm that the theoretical reversible capacity of the Mn3O4 filling is fully accessible. Upon reversible cycling, the Mn3O4@CNT nanocomposite reaches a maximum discharge capacity of 461 mA h g-1 at 100 mA g-1 with a capacity retention of 90% after 50 cycles. We attribute the good cycling stability to the hybrid nature of the nanocomposite: (1) Carbon encasements ensure electrical contact to the active material by forming a stable conductive network which is unaffected by potential cracks of the encapsulate. (2) The CNT shells resist strong volume changes of the encapsulate in response to electrochemical cycling, which in conventional (i.e., non-nanocomposite) Mn3O4 hinders the application in energy storage devices. Our results demonstrate that Mn3O4 nanostructures can be successfully grown inside CNT and the resulting nanocomposite can be reversibly converted and exploited for lithium-ion batteries.

A Three-Pronged Attack To Investigate the Electronic Structure of a Family of Ferromagnetic Fe4Ln2 Cyclic Coordination Clusters: A Combined Magnetic Susceptibility, High-Field/High-Frequency Electron Paramagnetic Resonance, and 57Fe Mössbauer Study.

We present the synthesis, structure, magnetic properties, as well as the Mössbauer and electron paramagnetic resonance studies of a ring-shaped [FeIII4LnIII2(Htea)4(µ-N3)4(N3)3(piv)3] (Ln = Y 1, Gd 2, Tb 3, Dy 4, Ho 5, Er, 6) coordination cluster. The Dy, Tb, and Ho analogues show blocking of the magnetization at low temperatures without applied fields. The anisotropy of the 3d ion and the exchange interaction between 3d and 4f ions in Fe4Ln2 complexes are unambiguously determined by high-field/high-frequency electron paramagnetic resonance measurements at low temperature. Ferromagnetic exchange interaction JFe-Ln is found which decreases upon variation of the Ln ions to larger atomic numbers. This dependence is similar to the behavior shown in the effective barrier values of complexes 3-5. Further information about the anisotropy of the Ln3+ ions was gathered with 57Fe Mössbauer spectroscopy, and the combination of these methods provides detailed information regarding the electronic structure of these complexes.

Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes.

A series of seven isostructural homodinuclear lanthanide complexes are reported. The magnetic properties (ac and dc SQUID measurements) are discussed on the basis of the X-ray structural properties which show that the two lanthanide sites are structurally different. MCD spectroscopy of the dysprosium(III) and neodymium(III) complexes ([Dy(III)2(L)(OAc)4](+) and [Nd(III)2(L)(OAc)4](+)) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([Gd(III)2(L)(OAc)4](+)) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([Dy(III)2(L)(OAc)4](+)), involving an ab initio (CASSCF) wave function, explicit spin-orbit coupling (RASSI-SO), and a ligand field analysis (Lines model and Stevens operators), is in full agreement with all experimental data (SQUID, HF-EPR, MCD) and specifically allowed us to accurately simulate the experimental χT versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways.

New phase of MnSb2O6 prepared by ion exchange: structural, magnetic, and thermodynamic properties.

A new layered trigonal (P3̅1m) form of MnSb2O6, isostructural with MSb2O6 (M = Cd, Ca, Sr, Pb, and Ba) and MAs2O6 (M = Mn, Co, Ni, and Pd), was prepared by ion-exchange reaction between ilmenite-type NaSbO3 and MnSO4-KCl-KBr melt at 470 °C. It is characterized by Rietveld analysis of the X-ray diffraction pattern, electron microprobe analysis, magnetic susceptibility, specific heat, and ESR measurements as well as by density functional theory calculations. MnSb2O6 is very similar to MnAs2O6 in the temperature dependence of their magnetic susceptibility and spin exchange interactions. The magnetic susceptibility and specific heat data show that MnSb2O6 undergoes a long-range antiferromagnetic order with Néel temperature TN = 8.5(5) K. In addition, a weak ferromagnetic component appears below T1 = 41.5(5) K. DFT+U implies that the main spin exchange interactions are antiferromagnetic, thereby forming spin-frustrated triangles. The long-range ordered magnetic structure of MnSb2O6 is predicted to be incommensurate as found for MnAs2O6. On heating, the new phase transforms to the stable P321 form via its intermediate disordered variant.

Synthesis and toxicity characterization of carbon coated iron oxide nanoparticles with highly defined size distributions.

BACKGROUND: Iron oxide nanoparticles hold great promise for future biomedical applications. To this end numerous studies on iron oxide nanoparticles have been conducted. One aspect these studies reveal is that nanoparticle size and shape can trigger different cellular responses through endocytic pathways, cell viability and early apoptosis. However, systematic studies investigating the size dependence of iron oxide nanoparticles with highly defined diameters across multiple cells lines are not available yet. METHODS: Iron oxide nanoparticles with well-defined size distributions were prepared. All samples were thoroughly characterized and the cytotoxicity for four standard cell lines (HeLa Kyoto, human osteosarcoma (U2OS), mouse fibroblasts (NIH 3T3) and mouse macrophages (J7442)) where investigated. RESULTS: Our findings show that small differences in size distribution (ca. 10nm) of iron oxide nanoparticles do not influence cytotoxicity, while uptake is size dependent. Cytotoxicity is dose-dependent. Broad distributions of nanoparticles are more easily internalized as compared to the narrow distributions for two of the cell lines tested (HeLa Kyoto and mouse macrophages (J7442)). CONCLUSION: The data indicate that it is not feasible to probe changes in cytotoxicity within a small size range (10nm). However, TEM investigations of the nanoparticles indicate that cellular uptake is size dependent. GENERAL SIGNIFICANCE: The present work compares narrow and broad distributions for various samples of carbon-coated iron oxide nanoparticles. The data highlights that cells differentiate between nanoparticle sizes as indicated by differences in cellular uptake. This information provides valuable knowledge to better understand the interaction of nanoparticles and cells.

Few-layer graphene shells and nonmagnetic encapsulates: a versatile and nontoxic carbon nanomaterial.

In this work a simple and scalable approach to coat nonmagnetic nanoparticles with few-layer graphene is presented. In addition, the easy processing of such nanoparticles to remove their core, leaving only the 3D graphene nanoshell, is demonstrated. The samples are comprehensively characterized, as are their versatility in terms of functionalization and as a material for electrochemical storage. Indeed, these 3D graphene nanostructures are easily functionalized much as is found with carbon nanotubes and planar graphene. Electrochemical investigations indicate these nanostructures are promising for stable long-life battery applications. Finally, initial toxicological investigations suggest no acute health risk from these 3D graphene nanostructures.

Morphology and agglomeration control of LiMnPO4 micro- and nanocrystals.

Microwave-assisted hydrothermal synthesis was used to grow LiMnPO4 micro- and nanocrystals from acetate precursors. By appropriate adjustment of the precursor concentration and the pH-value of the reactant, the product composition and purity along with the crystal size can be manipulated, resulting in particle-dimensions from around 10 µm down to a few 100 nm. Prisms and plates with hexagonal basal faces as well as cuboid and rod-like particles were produced. The effects on the crystal morphology as well as on the materials texture and agglomeration tendency are discussed and a comprehensive agglomeration phase diagram is constructed.

Chemisorption of exchange-coupled [Ni2L(dppba)]+ complexes on gold by using ambidentate 4-(diphenylphosphino)benzoate co-ligands.

A new strategy for the fixation of redox-active dinickel(II) complexes with high-spin ground states to gold surfaces was developed. The dinickel(II) complex [Ni2L(Cl)]ClO4 (1ClO4), in which L(2-) represents a 24-membered macrocyclic hexaaza-dithiophenolate ligand, reacts with ambidentate 4-(diphenylphosphino)benzoate (dppba) to form the carboxylato-bridged complex [Ni2L(dppba)](+), which can be isolated as an air-stable perchlorate [Ni2L(dppba)]ClO4 (2ClO4) or tetraphenylborate [Ni2L(dppba)]BPh4 (2BPh4) salt. The auration of 2ClO4 was probed on a molecular level, by reaction with AuCl, which leads to the monoaurated Ni(II)2Au(I) complex [Ni(II)2L(dppba)Au(I)Cl]ClO4 (3ClO4). Metathesis of 3ClO4 with NaBPh4 produces [Ni(II)2L(dppba)Au(I)Ph]BPh4 (4BPh4), in which the Cl(-) is replaced by a Ph(-) group. The complexes were fully characterized by ESI mass spectrometry, IR and UV/Vis spectroscopy, X-ray crystallography (2BPh4 and 4BPh4), cyclic voltammetry, SQUID magnetometry and HF-ESR spectroscopy. Temperature-dependent magnetic susceptibility measurements reveal a ferromagnetic coupling J = +15.9 and +17.9 cm(-1) between the two Ni(II) ions in 2ClO4 and 4BPh4 (H = -2 JS1S2). HF-ESR measurements yield a negative axial magnetic anisotropy (D<0), which implies a bistable (easy axis) magnetic ground state. The binding of the [Ni2L(dppba)]ClO4 complex to gold was ascertained by four complementary surface analytical methods: contact angle measurements, atomic-force microscopy, X-ray photoelectron spectroscopy, and spectroscopic ellipsometry. The results indicate that the complexes are attached to the Au surface through coordinative Au-P bonds in a monolayer.