Solvent Ligand Research Articles

Predictive Modeling of Nanocrystal Orientation in Superlattices: Insights from Ligand Entropy.

The self-assembly of nanocrystals (NCs) into close-packed, ordered superlattices (SLs) is of broad, engineering interest. The coherent orientation of polyhedral nanocrystals within NC SLs enhances electronic, magnetic, and vibrational coupling, leading to a variety of emergent phenomena. Here, we show that coherent orientation of polyhedral NCs in many SLs can be understood simply by considering its effect on the conformational entropy of surface ligands. We report the predicted nanocrystal orientations and entropic driving force to orient for a broad range of nanocrystal shapes and superlattice unit cells, and we show that ligand entropy is sufficient to reproduce a host of reported experimental and computational observations. We additionally use this framework to predict the expected distribution of interstitial species such as solvent or unbound ligands in an oriented NC SL. This work offers intuition for understanding the orientation of NCs in superlattices and a future framework for analyzing multinary structures.

A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

AbstractHybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in‐depth structure‐property relations, we report here a new family of 21 zero‐dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo‐octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual‐band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue‐light‐excitable single‐band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.

A Luminescent Hybrid Bimetallic Halide Family with Solvent-Coordinated Rare Earth and Alkaline Earth Metals.

Hybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in-depth structure-property relations, we report here a new family of 21 zero-dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo-octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual-band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue-light-excitable single-band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.

Stereocontrolled Synthesis of Aryl C-Nucleosides under Ambient Conditions.

A stereocontrolled synthesis of an aryl C-nucleoside has been developed using D-ribals and arylboronic acids catalyzed by palladium without additional ligands in common solvents under an open-air atmosphere at room temperature. This protocol features very mild conditions, simplicity in operation, exclusive β-stereoselectivity, broad substrate scopes, and good compatibility with reactive amino and hydroxyl groups. The functionalization of unsaturated C-nucleosides and the late-stage glycosylation of natural products/drugs demonstrated the high practicality of this strategy.

Initial Steps in Methanobactin Biosynthesis: Substrate Binding by the Mixed-Valent Diiron Enzyme MbnBC.

The MbnBC enzyme complex converts cysteine residues in a peptide substrate, MbnA, to oxazolone/thioamide groups during the biosynthesis of copper chelator methanobactin (Mbn). MbnBC belongs to the mixed-valent diiron oxygenase (MVDO) family, of which members use an Fe(II)Fe(III) cofactor to react with dioxygen for substrate modification. Several crystal structures of the inactive Fe(III)Fe(III) form of MbnBC alone and in complex with MbnA have been reported, but a mechanistic understanding requires determination of the oxidation states of the crystallographically observed Fe ions in the catalytically active Fe(II)Fe(III) state, along with the site of MbnA binding. Here, we have used electron nuclear double resonance (ENDOR) spectroscopy to determine such structural and electronic properties of the active site, in particular, the mode of substrate binding to the MV state, information not accessible by X-ray crystallography alone. The oxidation states of the two Fe ions were determined by 15N ENDOR analysis. The presence and locations of both bridging and terminal exogenous solvent ligands were determined using 1H and 2H ENDOR. In addition, 2H ENDOR using an isotopically labeled MbnA substrate indicates that MbnA binds to the Fe(III) ion of the cluster via the sulfur atom of its N-terminal modifiable cysteine residue, with displacement of a coordinated solvent ligand as shown by complementary 1H ENDOR. These results, which underscore the utility of ENDOR in studying MVDOs, provide a molecular picture of the initial steps in Mbn biosynthesis.

High-Efficiency Pure-Red CsPbI3 Quantum Dot Light-Emitting Diodes Enabled by Strongly Electrostatic Potential Solvent and Sequential Ligand Post-treatment Process.

Efficient pure-red emission light-emitting diodes (LEDs) are essential for high-definition displays, yet achieving pure-red emission is hindered by challenges like phase segregation and spectral instability when using halide mixing. Additionally, strongly confined quantum dots (QDs) produced through traditional hot-injection methods face byproduct contamination due to poor solubility of metal halide salts in the solvent octadecene (ODE) at low temperatures. Herein, we introduced a novel method using a benzene-series strongly electrostatic potential solvent instead of ODE to prevent PbI2 intermediates and promote their dissolution into [PbI3]-. Increasing methyl groups on benzene yields precisely sized (4.4 ± 0.1 nm) CsPbI3 QDs with exceptional properties: a narrow 630 nm PL peak with photoluminescence quantum yield (PLQY) of 97%. Sequential ligand post-treatment optimizes optical and electrical performance of QDs. PeLEDs based on optimized QDs achieve pure-red EL (CIE: 0.700, 0.290) approaching Rec. 2020 standards, with an EQE of 25.2% and T50 of 120 min at initial luminance of 107 cd/m2.

Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets.

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4fn systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT(μ-Me)(THF)]2 (2) and the nearly linear Li[(ErCOT)2(μ-Me)3] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT(Bn)(THF)2 (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin-vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased.

Effects of Temperature, Axial Ligand, and Photoexcitation on the Structure and Spin-State of Nickel(II) Complexes with Water-Soluble 5,10,15,20-Tetrakis(1-methylpyridinium-4-yl)porphyrin.

Water-soluble metalloporphyrins, depending on the metal center, possess special spectral, coordination, and photochemical features. In nickel(II) porphyrins, the Ni(II) center can occur with low-spin or high-spin electronic configuration. In aqueous solution, the cationic nickel(II) complex (Ni(II)TMPyP4+, where H2TMPyP4+ = 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin), exists in both forms in equilibrium. In this study, an equilibrium system involving the low-spin and high-spin forms of Ni(II)TMPyP4+ was investigated via application of irradiation, temperature change, and various potential axial ligands. Soret band excitation of this aqueous system, in the absence of additional axial ligands, resulted in a shift in the equilibrium toward the low-spin species due to the removal of axial solvent ligands. The kinetics and the thermodynamics of the processes were also studied via determination of the rate and equilibrium constants, as well as the ΔS, ΔH, and ΔG values. Temperature increase had a similar effect. The equilibrium of the spin isomers was also shifted by decreasing the solvent polarity (using n-propanol) as well as by the addition of a stronger coordinating axial ligand (such as ammonia). Since triethanolamine is an efficient electron donor in Ni(II)TMPyP4+-based photocatalytic systems, its interaction with this metalloporphyin was also studied. The results promote the development of efficient photocatalytic systems based on this complex.

Arresting dissolution of two-dimensional metal-organic frameworks enables long life in electrochemical devices.

Two-dimensional conjugated metal-organic frameworks (2D cMOFs) are emerging as promising materials for electrochemical energy storage (EES). Despite considerable interest, an understanding of their electrochemical stability and the factors contributing to their degradation during cycling is largely lacking. Here we investigate three Cu-based MOFs and report that the dissolution of 2D cMOFs into electrolytes is a prevalent and significant degradation pathway. Several factors, such as the inherent solubility of ligands in electrolyte solvents and the duration of charge-discharge cycling exert a strong influence on the dissolution process. When these factors combine within a MOF, severely limited cycling stability is observed, with dissolution accounting for up to 80% of capacity degradation. Conversely, excellent cycling stability is observed when testing a Cu-MOF with a sparingly soluble ligand within an optimized potential window. Overall, these findings represent essential insights into the electrochemical stability of 2D cMOFs, offering crucial guidelines for their targeted development in EES applications.

Effect of ion to ligand ratio on the aqueous to organic relative solubility of a lanthanide-ligand complex.

In the solvent extraction of rare earth elements, mechanistic aspects remain unclear regarding where and how extractant molecules coordinate metal ions and transport them from the aqueous phase into the organic phase. Molecular dynamics simulations were used to examine how unprotonated di(2-ethylhexyl)phosphoric acid (DEHP-) ligands that coordinate the Gd3+ ion can transfer the ion across the water-organic interface. Using the umbrella sampling technique, potential of mean force profiles were constructed to quantify the relative solubility of the Gd3+ ion coordinated to 0-3 DEHP- ligands in either water, 1-octanol, or hexane solvents and at the water-organic interfaces. The simulations show the Gd-DEHP- complexes, at varying Ln-ligand ratios, preferentially solvate on water-organic interfaces. While the Gd(DEHP-)3 complex will diffuse past the aqueous-organic interface into the octanol solvent, it is thermodynamically preferred for the Gd(DEHP-)3 complex to remain in the water-hexane interface when there is no amphiphilic layer of excess ligand.

Three-body interaction of gold nanoparticles: the role of solvent density and ligand shell orientation.

Molecular dynamics simulations are used to study the effective interactions of alkanethiol passivated gold nanoparticles in supercritical ethane at two- and three-particle levels with different solvent densities. Effective interaction is calculated as the potential of mean force (PMF) between two nanoparticles, and the three-body effect is estimated as the difference in PMFs calculated at the two- and three-particle levels. The variation in the three-body effect is examined as a function of solvent density. It is found that effective interaction, which is completely repulsive at very high solvent concentrations, progressively turns attractive as solvent density declines. On the other hand, the three-body effect turns out to be repulsive and increases exponentially with decreasing solvent density. Further, the structure of the ligand shell is analyzed as a function of nanoparticle separation, and its relationship with the three-body effect is investigated. It is observed that the three-body effect arises when the ligand shell begins to deform due to van der Waals repulsion between ligand shells. The study provides a deep insight into good understanding of the solvent evaporation-assisted nanoparticle self-assembly and can aid in experiments.

New copper carboxyl-ate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization.

Two new copper dimers, namely, bis-(dimethyl sulfoxide)-tetra-kis-(μ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO-)4(DMSO)2] (1), and bis-(di-methyl-formamide)-tetra-kis-(μ-pyrene-1-carboxyl-ato)dicopper(Cu-Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO-)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carb-oxy-lic acid, copper(II) nitrate and tri-ethyl-amine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group P , the crystal structure of 2 is in space group P21/n. The Cu atoms have octa-hedral geometries, with four oxygen atoms from carboxyl-ate pyrene ligands occupying the equatorial positions, a solvent mol-ecule coordinating at one of the axial positions, and a Cu⋯Cu contact in the opposite position. The packing in the crystal structures exhibits π-π stacking inter-actions and short contacts through the solvent mol-ecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the inter-molecular inter-actions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

Effect of solvent and auxiliary ligand on catecholase activities of Mn(III) complexes: A comparative study

A mononuclear Mn(III) complex with composition [MnIIIL(Cl)] (1) has been utilized to prepare two new complexes, [MnIIIL(N3)(CH3OH)] (2) and [MnIIIL(μ1,3-NCS)]n (3), by substitution of the auxiliary ligand. The ligand utilized for preparation of 1 is a Schiff base (H2L), obtained by 2:1 condensation of 3-Chlorosalicylaldehyde and ethylene diamine in methanol. The chloride anion, present in the coordination sphere of the central metal ion in 1 has been replaced by two other auxiliary ligands, azide and thiocyanate, in 2 and 3, respectively. All of the three complexes behaved as bio-functional models of catechol oxidase toward oxidation of 3,5-di-tert butyl catechol (3,5-DTBC). A detailed kinetic investigations were carried out for 2 and 3 in methanol, acetonitrile and N,N′-Dimethyl formamide (DMF) separately and the corresponding turn-over numbers have been determined. The ESI-MS spectra of the substrate-catalyst mixtures in acetonitrile and methanol confirmed formation of catecholate bound Mn(III) intermediate in the mass spectral time scale. The progress of the catechol oxidation was monitored by 1H-NMR spectroscopy with the reaction mixtures containing complex-substrate ratio at 1:20 after stirring in acetonitrile as well as methanol at room temperature in open air. NMR spectral data confirmed completion of the process in 90 minutes and 45 minutes for 2 and 3, respectively. Notably, in absence of any of these complexes, aerobic oxidation of 3,5-DTBC to the corresponding quinone is negligible even after twenty four hours of mixing in the same solvent. This observation is a clear indicative of high catalytic efficiencies of the prepared complexes.

Ligands on Nanocrystal Surfaces, the 1H Nuclear Magnetic Resonance Fingerprint.

ConspectusSurfaces are an integral part of colloidal nanocrystals (NCs). Hence, understanding the binding and packing to NC surfaces of organic ligands, which are often used to stabilize NC colloids, is an essential aspect of the formation of NCs with desired chemical or physical properties. Since NCs lack a unique structure, not a single analytical technique can provide a complete description of the chemistry of NC surfaces. Even so, solution 1H nuclear magnetic resonance spectroscopy stands out as a unique method to study the organic ligand shell for its capability to distinguish between surface bound species and surface inactive residues from NC synthesis and purification.In this account, we first set the stage by highlighting the fingerprints of ligands bound to NCs in solution 1H NMR, which are broadened and shifted resonances, slow diffusion, and pronounced transfer of spin polarization between nearby protons. These characteristics enable bound ligands to be identified and quantified by 1D 1H NMR spectroscopy, diffusion-ordered spectroscopy (DOSY), and nuclear Overhauser effect spectroscopy (NOESY). Even so, we argue in a second part that much more insight in surface chemistry can be obtained from the in situ monitoring of ligand exchange processes. The chemical analysis of released compounds and the thermodynamic study of exchange equilibria provide a surprisingly detailed picture of the chemistry of the NC-ligand bond, the heterogeneity of binding sites, and the bunching of ligands on the NC surface. Multiple case studies are discussed to illustrate these different aspects of NC surface chemistry, where work on CdSe NCs in particular indicates that binding sites at facet edges are most vulnerable for ligand loss. While such weak binding sites are a liability for optoelectronic applications, they could offer an opportunity for catalysis. Moreover, the general character of the methodology introduced calls for realizing a broad, quantitative survey of NC-ligand interactions, well beyond the extensively studied case of CdSe NCs.In a third part, we address in more detail the line broadening that characterizes ligands bound to NCs, which results from a combination of reduced mobility and a diversity of chemical environments. Hence, chemical shift and line shape, or rates of transversal relaxation and interligand cross-relaxation, can all convey information on the ligand environment, especially when solvents are used that are chemically distinct from the ligand chain, such as aromatic versus aliphatic. Two examples that illustrate this point are the relation between line width and ligand solvation, where better solvated ligands yield more narrow resonances, and the possibility to identify different parts of the inhomogeneously broadened resonance with ligands bound on different locations at the NC surface. Interestingly, such results question the limits of NC size and ligand packing density at which the current bound-ligand paradigm, modest inhomogeneous broadening, will break down. Building on this question, we summarize in a final part the current status of NC ligand analysis by solution 1H NMR and outline directions for further research.

Classical Force Field Parameters for InP and InAs Quantum Dots with Various Surface Passivations.

Classical molecular dynamics (MD) simulations on realistic colloidal quantum dot (QD) systems are often hampered by missing force field (FF) parameters for an accurate description of the QD-ligand interface. However, such calculations are of major interest, specifically for studying the surface chemistry of colloidal nanocrystals. In this work, we have utilized a previously published stochastic optimization algorithm to obtain FF parameters for InP and InAs QDs capped by Cl, amine, carboxylate, and thiolate ligands. Our FF parameters are interfaced with well-established FFs for organic molecules, allowing for the simulation of InP and InAs QDs with a broad range of organic ligands in explicit apolar solvents. The quality of our FF parameters was assessed by comparing properties of the classical MD simulations with ab initio MD simulations and experimental and theoretical values from the literature.

Cobalt(II) complexes containing mefenamic acid with imidazole and pyridine based auxiliary ligands: Synthesis, structural investigation and cytotoxic evaluation

The interaction between CoCl2.6H2O and mefenamic acid (2-[(2,3-dimethylphenyl)amino]benzoic acid) in the presence of imidazole and pyridine based ligands resulted in the formation of [Co(mef)2(imi)2]; C-1, [Co(mef)2(nic)2(H2O)2].2H2O; C-2, [Co2(µ-H2O)(µ-mef-O,O')2(mef)2(py)4].CH3CN; C-3, and [Co2(µ-mef-O,O')4(apy)2].2CH3CN; C-4, (mef is monodentate mefenamato, µ-H2O is bridging aqua ligand, µ-mef-O, O' is bridging bidentate mefenamato, imi is imidazole, nic is nicotinamide, py is pyridine, and apy is 2-aminopyridine). The complexes were characterized spectroscopically and by physicochemical properties. Single-crystal X-ray diffraction studies confirmed the structures of the complexes. In C-1, Co(II) is in four-coordinate geometry, while in C-2, Co(II) is in hexa-coordination with two mefenamato carboxylate oxygen atoms, two nitrogen atoms, and two oxygen atoms from two solvent ligands. Complex C-3 consists of two cobalt centers linked by an aqua ligand and bridged by two mefenamato ligands. Furthermore, the octahedral geometry in each Co(II) in C-3 was completed by coordinating two monodentate mefenamato ligands and monodentate pyridine ligands. Similarly, in C-4, a Co-Co bond connects two Co(II) centers in six-coordinate geometry, with four bidentate mefenamato ligands acting as bridges between the two Co(II) and two 2-aminopyridine nitrogen, in monodentate coordination to each Co(II). The lattice solvents in C-2 to C-4 participated in intermolecular hydrogen bonding interactions with the mefenamato ligand. FTIR studies showed the presence of both monodentate and bidentate coordination of the deprotonated carboxylate oxygen atoms of the mefenamato ligand, as well as the coordination of the nitrogen donor ligands in the complexes. TG analysis determined the complexes' thermal stability and decomposition steps and ascertained their compositions, which agreed with the analytical and X-ray crystallography studies. Furthermore, the cytotoxicity of mefenamic acid and the cobalt (II) complexes on lung carcinoma cells (NCIH-460) and breast cells (MDAMB) were assessed using MTT assay. The complexes showed higher cytotoxicity than mefenamic acid against the MDAMB cell line.

Anisotropic Friction in a Ligand-Protein Complex.

The effect of an externally applied directional force on molecular friction is so far poorly understood. Here, we study the force-driven dissociation of the ligand-protein complex biotin-streptavidin and identify anisotropic friction as a not yet described type of molecular friction. Using AFM-based stereographic single molecule force spectroscopy and targeted molecular dynamics simulations, we find that the rupture force and friction for biotin-streptavidin vary with the pulling angle. This observation holds true for friction extracted from Kramers' rate expression and by dissipation-corrected targeted molecular dynamics simulations based on Jarzynski's identity. We rule out ligand solvation and protein-internal friction as sources of the angle-dependent friction. Instead, we observe a heterogeneity in free energy barriers along an experimentally uncontrolled orientation parameter, which increases the rupture force variance and therefore the overall friction. We anticipate that anisotropic friction needs to be accounted for in a complete understanding of friction in biomolecular dynamics and anisotropic mechanical environments.

Nickel Boride (NixB) Nanocrystals: From Solid-State Synthesis to Highly Colloidally Stable Inks

Metal borides, a class of materials intensively used in industry as superconductors, magnetic materials, or hot cathodes, remain largely unexplored at the nanoscale mainly due to the difficulty in synthesizing single-phase nanocrystals. Recent works have shown that synthetic methods at lower temperatures (<400 °C) yield amorphous polydisperse nanoparticles, while phase purity is an issue at higher temperatures. Among all the metal-rich borides, nickel borides (NixB) could be a potential catalyst for a broad range of applications (hydrogenations, electrochemical hydrogen, and oxygen evolution reactions) under challenging conditions (such as high pH or high temperatures). Here, we report a novel solid-state method to synthesize NixB nanopowders (with a diameter of approximately 45 nm) and their conversion into colloidal suspensions (inks) through treatment of the nanocrystal surface. For the solid-state synthesis, we used commercially available salts and explored the reaction between the Ni and B sources while varying the synthetic parameters under mild and solvent-free reaction conditions. We show that pure phase Ni3B and Ni2B NCs can be obtained with high yield in the pure phase using as precursors NiCl2 and Ni, respectively. Through extensive mechanistic studies, we show that Ni nanoclusters (1–2 nm) are an intermediate in the boriding process, while the metal co-reactant lowers the decomposition temperature of NaBH4 (used as a reducing agent and B source). Size control can instead be exerted through reaction mediators, as seen from the differential nucleation and growth of Ni (clusters) or NixB NCs when employing L- (amine, phosphine) and X-type (carboxylate) mediators. Applying surface engineering methods to our NixB NCs, we stabilized them with inorganic (NOBF4) or organic (borane tert-butyl amine, oleylamine) ligands in the appropriate solvent (DMSO, hexane). With this method, we produce stable inks for further solution processing applications. Our results provide tools for further development of catalysts based on NixB NCs and pave the way for synthesizing other metal boride colloidal nanostructures.

Solvent Coligand-Induced Spin State Variation in Iron(II) Complexes Bearing Pentadentate N5 Ligand Toward the Construction of an N5O Spin Crossover Center

Three iron(II) complexes having a 1,2,3-triazole-containing linear pentadentate N5 ligand L3-Me-3Me and different monodentate solvent coligand X, [Fe(L3-Me-3Me)X](BPh4)2 [L3-Me-3Me = bis(N,N′-1-methyl-1H-1,2,3-triazol-4-yl-methylideneaminopropyl)methylamine; X = MeCN (1), dimethylformamide (DMF) (2), and dimethyl sulfoxide (DMSO) (3)] have been selectively prepared by the choice of reaction solvent. Along the well-known spectrochemical series, the strong-field solvent ligand MeCN generates a low-spin (LS) complex 1, the weak-field ligand DMSO generates a high-spin (HS) complex 3, and the complex 2 coordinated by the medium-field ligand DMF exhibits gradual and reversible one-step HS↔LS spin crossover (SCO) with T1/2 = 173 K in the temperature range of 400–5 K. This spin state variation among LS 1, HS 3, and SCO 2 has been investigated by the combination of temperature-dependent magnetic susceptibilities measurements, single-crystal X-ray diffraction (SCXRD) studies, Hirshfeld surface analyses, and density functional theory calculations. In addition, the details of structural change between HS and LS states of an N5O iron(II) center upon SCO are revealed for the first time by the variable-temperature SCXRD studies for 2 at nine different temperatures in which the difference of Fe–O bond length between the two spin states is shorter than that of any other Fe–N bond lengths.

Preferential Enrichment of Enantiomer from Amino Acid Schiff Bases by Coordination Interaction and Crystallization.

In this paper, preferential enrichment (PE) is described for three pairs of novel amino acid Schiff base Cu(II)/Cu(I) complexes. Single crystal X-ray diffraction indicated that 1-S/R are one-dimensional coordination polymers (CPs) with helical structures, and 2-S/R and 3-S/R are one-dimensional CPs with auxiliary ligands. By tuning the pH, the solvent and second ligands, the 1-S/R, 3-S/R underwent polymorphic transitions, resulting in enantioselective liberation of excess enantiomers into solution, until the deposited crystals were slightly enriched with the opposite enantiomer, thereby successfully exhibiting PE. However, under the effects of Cu(II), the solvent and low pH, 2-S/R did not exhibit PE and resulted in enrichment of racemic compounds, which was attributed to amino acid Schiff base chiral complex mechanisms of PE. The three pairs of Cu complex structures were characterized by UV-vis, MS and X-ray photoelectron spectroscopy (XPS). All chiral properties were studied by circular dichroism (CD) in the solid and liquid.