Solvent Coordination Research Articles

Picosecond infrared laser driven sample delivery for simultaneous liquid-phase and gas-phase electron diffraction studies.

Here, we report on a new approach based on laser driven molecular beams that provides simultaneously nanoscale liquid droplets and gas-phase sample delivery for femtosecond electron diffraction studies. The method relies on Picosecond InfraRed Laser (PIRL) excitation of vibrational modes to strongly drive phase transitions under energy confinement by a mechanism referred to as Desorption by Impulsive Vibrational Excitation (DIVE). This approach is demonstrated using glycerol as the medium with selective excitation of the OH stretch region for energy deposition. The resulting plume was imaged with both an ultrafast electron gun and a pulsed bright-field optical microscope to characterize the sample source simultaneously under the same conditions with time synchronization equivalent to sub-micrometer spatial resolution in imaging the plume dynamics. The ablation front gives the expected isolated gas phase, whereas the trailing edge of the plume is found to consist of nanoscale liquid droplets to thin films depending on the excitation conditions. Thus, it is possible by adjusting the timing to go continuously from probing gas phase to solution phase dynamics in a single experiment with 100% hit rates and very low sample consumption (<100 nl per diffraction image). This approach will be particularly interesting for biomolecules that are susceptible to denaturation in turbulent flow, whereas PIRL–DIVE has been shown to inject molecules as large as proteins into the gas phase fully intact. This method opens the door as a general approach to atomically resolving solution phase chemistry as well as conformational dynamics of large molecular systems and allow separation of the solvent coordinate on the dynamics of interest.

Stereocontrolled Synthesis of C20S-C26 and C20R-C26 Fragments of Amphidinolide L.

Amphidinolide L is a cytotoxic macrolide isolated from marine symbiotic dinoflagellates of the genus Amphidinium. While its planar structure and the absolute stereochemistry of the C21-C26 part have been determined, six stereocenters have remained unassigned. Aiming at structure determination, we have developed a synthetic route to the C20S-C26 and C20R-C26 fragments via the Li-mediated stereocontrolled aldol reaction. Two aldehydes, 16 with the C22-hydroxy group and 19 with the C22-TES ether, were synthesized from lactone 4. The aldol reactions using the Li-enolate of 4-methyl-2-pentanone in THF provided the C20S-C26 fragment 20 from 16 and a 1:3.5 mixture of the C20-C26 fragment 22 favoring the C20R-isomer. Mechanistic studies based on an extensive search of transition states in explicit solvents indicated that the C20S-isomer would be generated via a tri-solvated transition state, while the C20R-isomer would be formed via a di-solvated transition state. The calculation emphasizes the importance of the coordination network as a higher-order complex composed of solvent molecules, aldehyde, enolate, and Li atoms in the reaction of 16 to minimize steric interactions but maximize the stabilizing effect by the coordination of solvents. The presence of the rotationally free aldehyde in the reaction of 19 results in moderate diastereoselectivity.

Solvent-Dependent Oxidative Addition and Reductive Elimination of H2 Across a Gallium-Zinc Bond.

H2 adds reversibly across the metal‐metal bond of [(BDI)Ga(H)−Zn(tmeda)(thf)][BAr4 F] (BDI=[HC{C(CH3)N(2,6‐iPr2‐C6H3)}2]−, TMEDA=N,N,N′,N′‐tetramethylethylenediamine, BAr4 F−=[B(C6H3‐3,5‐(CF3)2)4]−). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH2] and [(tmeda)ZnH(thf)][BAr4 F] are favoured in THF solution, but THF‐free mixtures of [(BDI)GaH2] and [(tmeda)ZnH(OEt2)][BAr4 F] are predisposed towards entropically driven dehydrogenation to [(BDI)Ga(H)−Zn(tmeda)][BAr4 F] in fluorobenzene solution.

Tailoring Coordination in Conventional Ether‐Based Electrolytes for Reversible Magnesium‐Metal Anodes

AbstractRechargeable magnesium (Mg) batteries based on conventional electrolytes are seriously plagued by the formation of the ion‐blocking passivation layer on the Mg metal anode. By tracking the Mg2+ solvation sheath, this work links the passivation components to the Mg2+‐solvents (1,2‐dimethoxyethane, DME) coordination and the consequent thermodynamically unstable DME molecules. On this basis, we propose a methodology to tailor solvation coordination by introducing the additive solvent with extreme electron richness. Oxygen atoms in phosphorus‐oxygen groups compete with that in carbon‐oxygen groups of DME for the coordination with Mg2+, thus softening the solvation sheath deformation. Meanwhile, the organophosphorus molecules in the rearranged solvation sheath decompose on the Mg surface, increasing the Mg2+ transport and electrical resistance by three and one orders of magnitude, respectively. Consequently, the symmetric cells exhibit superior cycling performance of over 600 cycles with low polarization.

Tailoring Coordination in Conventional Ether-Based Electrolytes for Reversible Magnesium-Metal Anodes.

Rechargeable magnesium (Mg) batteries based on conventional electrolytes are seriously plagued by the formation of the ion-blocking passivation layer on the Mg metal anode. By tracking the Mg2+ solvation sheath, this work links the passivation components to the Mg2+ -solvents (1,2-dimethoxyethane, DME) coordination and the consequent thermodynamically unstable DME molecules. On this basis, we propose a methodology to tailor solvation coordination by introducing the additive solvent with extreme electron richness. Oxygen atoms in phosphorus-oxygen groups compete with that in carbon-oxygen groups of DME for the coordination with Mg2+ , thus softening the solvation sheath deformation. Meanwhile, the organophosphorus molecules in the rearranged solvation sheath decompose on the Mg surface, increasing the Mg2+ transport and electrical resistance by three and one orders of magnitude, respectively. Consequently, the symmetric cells exhibit superior cycling performance of over 600 cycles with low polarization.

Predicting the Ion Desolvation Pathway of Lithium Electrolytes and Their Dependence on Chemistry and Temperature.

To better understand the influence of electrolyte chemistry on the ion-desolvation portion of charge-transfer beyond the commonly applied techniques, we apply free-energy sampling to simulations involving diethyl ether (DEE) and 1,3-dioxoloane/1,2-dimethoxyethane (DOL/DME) electrolytes, which display bulk solvation structures dominated by ion-pairing and solvent coordination, respectively. This analysis was conducted at a pristine electrode with and without applied bias at 298 and 213 K to provide insights into the low-temperature charge-transfer behavior, where it has been proposed that desolvation dominates performance. We find that, to reach the inner Helmholtz layer, ion-paired structures are advantageous and that the Li+ ion must reach a total coordination number of 3, which requires the shedding of 1 species in the DEE electrolyte or 2-3 species in DOL/DME. This work represents an effort to predict the distinct thermodynamic states as well as the most probable kinetic pathways of ion desolvation relevant for the charge transfer at electrochemical interphases.

Stochastic Model of Solvent Exchange in the First Coordination Shell of Aqua Ions.

Ion microsolvation is a basic, yet fundamental, process of ionic solutions underlying many relevant phenomena in either biological or nanotechnological applications, such as solvent reorganization energy, ion transport, catalytic activity, and so on. As a consequence, it is a topic of extensive investigations by various experimental techniques, ranging from X-ray diffraction to NMR relaxation and from calorimetry to vibrational spectroscopy, and theoretical approaches, especially those based on molecular dynamics (MD) simulations. The conventional microscopic view of ion solvation is usually provided by a “static” cluster model representing the first ion–solvent coordination shell. Despite the merits of such a simple model, however, ion coordination in solution should be better regarded as a complex population of dynamically interchanging molecular configurations. Such a more comprehensive view is more subtle to characterize and often elusive to standard approaches. In this work, we report on an effective computational strategy aiming at providing a detailed picture of solvent coordination and exchange around aqua ions, thus including the main structural, thermodynamic, and dynamic properties of ion microsolvation, such as the most probable first-shell complex structures, the corresponding free energies, the interchanging energy barriers, and the solvent-exchange rates. Assuming the solvent coordination number as an effective reaction coordinate and combining MD simulations with enhanced sampling and master-equation approaches, we propose a stochastic model suitable for properly describing, at the same time, the thermodynamics and kinetics of ion–water coordination. The model is successfully tested toward various divalent ions (Ca2+, Zn2+, Hg2+, and Cd2+) in aqueous solution, considering also the case of a high ionic concentration. Results show a very good agreement with those issuing from brute-force MD simulations, when available, and support the reliable prediction of rare ion–water complexes and slow water exchange rates not easily accessible to usual computational methods.

Novel solvent-free energetic 3D metal-organic frameworks and their laser response

• Two new energetic complexes with the same topological structure were synthesized. • The complex has good thermal stability and detonation ability, and can detonate under laser stimulation. • Their laser response process is captured, which shows that the initiation threshold is less than 7 mJ. Two novel energetic metal–organic frameworks (EMOFs) were prepared by simple hydroxytetrazole (OH-Tz) method with hydroxytetrazole which have good oxygen balance and coordination ability as energetic ligand, namely, [Pb(OH-Tz) 2 ] n and [Pb(OH-Tz)(NO 3 )] n , were prepared by simple hydrothermal method. The two EMOFs have the same three-dimensional network structure, and there are no coordination solvent molecules in the structure, they form a dense network structure through the coordination bond length, so they have high density (3.578 and 4.154 g∙cm −3 , respectively), good thermal stability( T dec greater than 230 ℃) and detonation properties similar to those of RDX or HMX (8.62 km s −1 , 46.20 GPa and 8.13 km s −1 , 42.71 GPa, respectively). The response process of EMOFs to laser was captured by high-speed camera, and the initiation ability of EMOFs was tested by lead plate experiment, which shows that these solvent-free EMOFs have good laser-response performance and initiation ability.

The simulation of a green room-temperature ternary solution of water, methanol and 1-ethyl-3-methyl imidazolium chloride by all-atom Monte Carlo and DFT computational approaches

A highly dense ternary solution of water, methanol and 1-ethyl-3-methyl imidazolium chloride [emim][Cl] was investigated by a Monte Carlo (MC) program written in C language, Density Functional Theory (DFT) and Atoms-In-Molecules (AIM) theory. The all-atom approach in MC calculations of a ternary solution, the use of nonzero LJ parameters for all hydrogen atoms in simulation box and the creation of a new strategy for filling simulation box with many molecules were adopted in this research to yield a comprehensive, accurate and different work. The radial distribution function, the molar heat capacities in constant volume and pressure, the thermal expansivity, and the isothermal compressibility of the ternary system were calculated. The chemical potentials were calculated at different temperatures through Widom insertion method and the behaviors of both ideal and excess parts of chemical potentials were analyzed versus temperature. The value of electric permittivity of solution, the change of number of methanol and water molecules and the replacement of chloride anion with iodide in ionic liquid were also explored through separate simulations. The solvation structure and coordination number were investigated for various systems. The optimized sites for water and methanol around [emim]+ recognized by DFT and the HOMO and LUMO isosurfaces were discussed. Also, the hydrogen bonds between components of ternary solution were determined by AIM theory. It was shown that the results of quantum mechanics calculations confirm those of MC simulations.

Role of Solvent Coordination on the Structure and Dynamics of ansa-Zirconocenium Ion Pairs in Aromatic Hydrocarbons

The solution structure and dynamics of three prototypical bis-indenyl ansa-zirconocenium methyl cations (Me2Si(2-methyl-4-phenyl-6-tert-butylindenyl)2ZrMe+, [1Me]+; Me2Si(2,4-dimethylindenyl)2ZrMe+, [2Me]+; Me2Si(indenyl)2ZrMe+, [3Me]+) paired with the weakly coordinating B(C6F5)4– anion have been investigated by NMR spectroscopy in aromatic hydrocarbons with different polarities (toluene, εr = 2.38; chlorobenzene, εr = 5.69; 1,2-difluorobenzene (ODFB), εr = 13.38). These highly electrophilic cations are stabilized by solvent coordination, as evidenced by the unequivocal identification of [1Me·C7H8]+B(C6F5)4–, a rare example of a toluene-stabilized ion pair that has been fully characterized in solution. Combining spectroscopic and DFT methods allowed us to evaluate how solvent coordination modulates the dynamic processes typical of this class of catalysts. An exchange between the two faces of coordinated toluene (face inversion, FI) occurs without solvent decomplexation (ΔH⧧FI = 14.6 kcal mol–1; ΔS⧧FI = 3 cal mol–1 K–1; ΔG⧧FI(298) = 13.7 kcal mol–1) and is about 20 times faster than the exchange between coordinated and free solvent (solvent decomplexation, SD, ΔH⧧SD = 17.9 kcal mol–1; ΔS⧧SD = 10 cal mol–1 K–1; ΔG⧧SD(298) = 14.9 kcal mol–1) and ion pair symmetrization (IPS, ΔH⧧IPS = 18.6 kcal mol–1; ΔS⧧IPS = 12 cal mol–1 K–1; ΔG⧧IPS(298) = 14.9 kcal mol–1). For the ion pairs [1–3Me·solvent]+B(C6F5)4–, IPS rate constants (kIPS) do not correlate with the solvent polarity (kIPS(ODFB) > kIPS(toluene) > kIPS(chlorobenzene)). For the more coordinating toluene and chlorobenzene solvents, ΔG⧧IPS nicely tracks with the amount of positive charge at the metal, increasing as the positive charge increases (qZrMe2,CM5; 1Me2 > 3Me2 > 2Me2). In contrast, in the less coordinating ODFB, differences in the IPS barriers for [1–3Me·ODFB]+B(C6F5)4– appear to correlate better with steric parameters, as measured by the percent buried volume on the open quadrants (%VBur,open) for the corresponding neutral precursors (%VBur,open = 34.8, 35.5, 34.6% for 1Me2, 2Me2, and 3Me2, respectively).

Controlling the Direction of S-Nitrosation versus Denitrosation: Reversible Cleavage and Formation of an S-N Bond within a Dicopper Center.

Iron and copper enzymes are known to promote reversible S-nitrosation/denitrosation in biology. However, it is unclear how the direction of S-N bond formation/scission is controlled. Herein, we demonstrate the interconversion of metal-S-nitrosothiol adduct M(RSNO) and metal nitrosyl thiolate complex M(NO)(SR), which may regulate the direction of reversible S-(de)nitrosation. Treatment of a dicopper(I,I) complex with RSNO leads to a mixture of two structural isomers: dicopper(I,I) S-nitrosothiol [CuICuI(RSNO)]2+ and dicopper(II,II) nitrosyl thiolate [CuIICuII(NO)(SR)]2+. The Keq between these two structural isomers is sensitive to temperature, the solvent coordination ability, and counterions. Our study illustrates how copper centers can modulate the direction of RS-NO bond formation and cleavage through a minor perturbation of the local environment.

Generation of Strong Basicity in Metal-Organic Frameworks: How Do Coordination Solvents Matter?

Solid strong bases with an ordered pore structure (OPS-SSBs) have attracted much attention because of their high catalytic activity and shape selectivity as heterogeneous catalysts in various reactions. Nevertheless, high temperatures are required to fabricate OPS-SSBs by using traditional methods. Herein, we report for the first time that the coordination solvents affect basicity generation in metal-organic frameworks (MOFs) greatly and that strong basicity can be formed at comparatively low temperatures. A typical MOF, MIL-53, was employed, and three different solvents, namely, water, methanol, and N,N-dimethylformamide (DMF), were coordinated, respectively, by means of solvent exchange. Thermogravimetry-mass spectrometer analysis shows that the conversion temperature of base precursor KNO3 is quite different on MIL-53 coordinated with different solvents. The conversion of KNO3 to basic sites takes place at 350, 300, and 250 °C on MIL-53 coordinated with water, methanol, and DMF, respectively. It is fascinating to observe the generation temperature of strongly basic sites at 250 °C, which is noticeably lower than that on various supports, such as mesoporous silica SBA-15 (600 °C), zeolite Y (700 °C), and metal oxide ZrO2 (730 °C). This is due to the redox interaction between coordination solvents and KNO3, leading to a significant decrease in the temperature for KNO3 conversion. Consequently, OPS-SSBs were prepared successfully with an ordered pore structure and strong basicity. The obtained OPS-SSBs show good shape selectivity in Knoevenagel condensation of aromatic aldehydes with different active methylene compounds. Moreover, these solid bases are highly active in the synthesis of dimethyl carbonate through transesterification reaction. This work might open up a new avenue for the fabrication of various functional materials at low temperatures through redox interactions.

Effect of the Ancillary Ligand on the Performance of Heteroleptic Cu(I) Diimine Complexes as Dyes in Dye-Sensitized Solar Cells.

A series of heteroleptic Cu(I) diimine complexes with different ancillary ligands and 6,6′-dimethyl-2,2′-bipyridine-4,4′-dibenzoic acid (dbda) as the anchoring ligand were self-assembled on TiO2 surfaces and used as dyes for dye-sensitized solar cells (DSSCs). The binding to the TiO2 surface was studied by hard X-ray photoelectron spectroscopy for a bromine-containing complex, confirming the complex formation. The performance of all complexes was assessed and rationalized on the basis of their respective ancillary ligand. The DSSC photocurrent–voltage characteristics, incident photon-to-current conversion efficiency (IPCE) spectra, and calculated lowest unoccupied molecular orbital (LUMO) distributions collectively show a push–pull structural dye design, in which the ancillary ligand exhibits an electron-donating effect that can lead to improved solar cell performance. By analyzing the optical properties of the dyes and their solar cell performance, we can conclude that the presence of ancillary ligands with bulky substituents protects the Cu(I) metal center from solvent coordination constituting a critical factor in the design of efficient Cu(I)-based dyes. Moreover, we have identified some components in the I–/I3–-based electrolyte that causes dissociation of the ancillary ligand, i.e., TiO2 photoelectrode bleaching. Finally, the detailed studies on one of the dyes revealed an electrolyte–dye interaction, leading to a dramatic change of the dye properties when adsorbed on the TiO2 surface.

Ir(IV) Sulfoxide-Pincer Complexes by Three-Electron Oxidative Additions of Br2 and I2. Unprecedented Trap-Free Reductive Elimination of I2 from a formal d5 Metal.

Oxidative addition of 1.5 equiv of bromine or iodine to a Ir(I) sulfoxide pincer complex affords the corresponding Ir(IV) tris-bromido or tris-iodido complexes, respectively. The unprecedented trap-free reductive elimination of iodine from the Ir(IV)-iodido complex is induced by coordination of ligands or donor solvents. In the case of added I-, the isostructural tris-iodo Ir(III)-ate complex is quickly generated, which then can be readily reoxidized to the Ir(IV)-iodido complex with FcPF6 or electrochemically. DFT calculations indicate an "inverted ligand field" in the Ir(IV) complexes and favor dinuclear pathways for the reductive elimination of iodine from the formal d5 metal center.

Biomimetic control of charge transfer in MOFs by solvent coordination for boosting photocatalysis.

The role of the coordination solvent in MOFs with photocatalysis can't be ignored. Novel [Ni(PTCA)·sol]-MOFs with a 3D open wavy-layered structure are selected for in-depth study by imitating the internal environment of a chameleon. The results confirm that the coordination solvent can modulate the band structure and the polarity is the key to accelerate the formation of intermediate H*.

Solvent coordination to palladium can invert the selectivity of oxidative addition.

Reaction solvent was previously shown to influence the selectivity of Pd/PtBu3-catalyzed Suzuki–Miyaura cross-couplings of chloroaryl triflates. The role of solvents has been hypothesized to relate to their polarity, whereby polar solvents stabilize anionic transition states involving [Pd(PtBu3)(X)]− (X = anionic ligand) and nonpolar solvents do not. However, here we report detailed studies that reveal a more complicated mechanistic picture. In particular, these results suggest that the selectivity change observed in certain solvents is primarily due to solvent coordination to palladium. Polar coordinating and polar noncoordinating solvents lead to dramatically different selectivity. In coordinating solvents, preferential reaction at triflate is likely catalyzed by Pd(PtBu3)(solv), whereas noncoordinating solvents lead to reaction at chloride through monoligated Pd(PtBu3). The role of solvent coordination is supported by stoichiometric oxidative addition experiments, density functional theory (DFT) calculations, and catalytic cross-coupling studies. Additional results suggest that anionic [Pd(PtBu3)(X)]− is also relevant to triflate selectivity in certain scenarios, particularly when halide anions are available in high concentrations.

Rational solvent molecule tuning for high-performance lithium metal battery electrolytes

Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amount of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar –CHF2 is identified as the optimal group rather than fully fluorinated –CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+–solvent coordination, solvation environments and battery performance is investigated to understand structure–property relationships.

Non-innocent redox behavior of CuII-p-dimethylaminophenolate complexes: formation and characterization of the CuI-phenoxyl radical species.

Cu complexes with p-dimethylaminophenolate ligands were synthesized by the reaction of CuII ions with the ligands under inert gas atmosphere and characterized. The complexes showed a valence state change from CuII-phenolate to CuI-phenoxyl radical on loss of the coordinated solvent. The CuI-phenoxyl radical species showed the characteristic properties and reactivities.

Engineering lanmodulin's selectivity for actinides over lanthanides by controlling solvent coordination and second-sphere interactions.

Developing chelators that combine high affinity and selectivity for lanthanides and/or actinides is paramount for numerous industries, including rare earths mining, nuclear waste management, and cancer medicine. In particular, achieving selectivity between actinides and lanthanides is notoriously difficult. The protein lanmodulin (LanM) is one of Nature's most selective chelators for trivalent actinides and lanthanides. However, mechanistic understanding of LanM's affinity and selectivity for f-elements remains limited. In order to decipher, and possibly improve, the features of LanM's metal-binding sites that contribute to this actinide/lanthanide selectivity, we characterized five LanM variants, substituting the aspartate residue at the 9th position of each metal-binding site with asparagine, histidine, alanine, methionine, and selenomethionine. Spectroscopic measurements with lanthanides (Nd3+ and Eu3+) and actinides (243Am3+ and 248Cm3+) reveal that, contrary to the behavior of small chelator complexes, metal-coordinated water molecules enhance LanM's affinity for f-elements and pH-stability of its complexes. Furthermore, the results show that the native aspartate does not coordinate the metal directly but rather hydrogen bonds to coordinated solvent. By tuning this first-sphere/second-sphere interaction, the asparagine variant nearly doubles LanM's selectivity for actinides versus lanthanides. This study not only clarifies the essential role of coordinated solvent for LanM's physiological function and separation applications, but it also demonstrates that LanM's preference for actinides over lanthanides can be further improved. More broadly, it demonstrates how biomolecular scaffolds possess an expanded repertoire of tunable interactions compared to most small-molecule ligands – providing an avenue for high-performance LanM-based actinide/lanthanide separation methods and bio-engineered chelators optimized for specific medical isotopes.

Size Control in the Colloidal Synthesis of Plasmonic Magnesium Nanoparticles.

Nanoparticles of plasmonic materials can sustain oscillations of their free electron density, called localized surface plasmon resonances (LSPRs), giving them a broad range of potential applications. Mg is an earth-abundant plasmonic material attracting growing attention owing to its ability to sustain LSPRs across the ultraviolet, visible, and near-infrared wavelength range. Tuning the LSPR frequency of plasmonic nanoparticles requires precise control over their size and shape; for Mg, this control has previously been achieved using top-down fabrication or gas-phase methods, but these are slow and expensive. Here, we systematically probe the effects of reaction parameters on the nucleation and growth of Mg nanoparticles using a facile and inexpensive colloidal synthesis. Small NPs of 80 nm were synthesized using a low reaction time of 1 min and ∼100 nm NPs were synthesized by decreasing the overall reaction concentration, replacing the naphthalene electron carrier with biphenyl or using metal salt additives of FeCl3 or NiCl2 at longer reaction times of 17 h. Intermediate sizes up to 400 nm were further selected via the overall reaction concentration or using other metal salt additives with different reduction potentials. Significantly larger particles of over a micrometer were produced by reducing the reaction temperature and, thus, the nucleation rate. We showed that increasing the solvent coordination reduced Mg NP sizes, while scaling up the reaction reduced the mixing efficiency and produced larger NPs. Surprisingly, varying the relative amounts of Mg precursor and electron carrier had little impact on the final NP sizes. These results pave the way for the large-scale use of Mg as a low-cost and sustainable plasmonic material.