Solid State Research Articles

A Strongly Reducing sp2 Carbon-Conjugated Covalent Organic Framework Formed by N-Heterocyclic Carbene Dimerization.

Covalent organic frameworks linked by carbon-carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp2 carbon-conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN-COF-1 (CORN = Cornell University), prepared by N-heterocyclic carbene (NHC) dimerization. In-depth characterization reveals that CORN-COF-1 possesses a two-dimensional layered structure and hexagonal guest-accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN-COF-1 to tetracyanoethylene (TCNE, E1/2 = 0.13 V and -0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE•- and the dianion TCNE2- as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE•- radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN-COF-1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox-active C=C COFs, paving the way for the design of novel materials.

Green formulation of Menadione-loaded niosome as a skin-lightening preparation: In vitro/In vivo safety evaluation on Wistar rat

Purpose: In the present research, a green technique (an ultrasonic method) was used to synthesize menadione sodium bisulfite (MSB) niosome (Menasome) which is used to improve dermal delivery and increase anti-melanogenesis activities. Methods: Various cholesterol: surfactant (Chol: Sur) ratios were investigated to optimize the Menasomes. Photon correlation spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC) were employed to characterize the solid state of MSB in nanoparticle form. Additionally, the optimized formulation was used to investigate ex-vivo skin absorption, in vivo skin irritation, in vitro cell survival, and anti-melanogenesis activity. Results: The results exhibited that increasing cholesterol (Chol) declined the average size of the Menasomes from 653.766±25.171 nm to 298.133±8.823 nm and increased entrapment efficiency 30.237±3.4204% to 83.616±2.550 %. The rat skin permeation study indicated that Menasome gel administered more MSB in dermal layers (439.000±36.190μg/cm2 or 23.827±1.964%) than MSB plain gel (286.200± 22.6μg/cm2 or 15.53±1.227%). In both the in vivo skin irritation test and the in vitro cytotoxicity experiment, the extended-release behavior of the enhanced Menasome demonstrated a minimal side effect profile. Furthermore, optimum Menasome inhibited melanin formation (37.426± 1.644% at 15μM) greater than free MSB (57.383±1.654%) considerably (p <0.05). Furthermore, Menasome 7 prevented L-dopa auto-oxidation in higher levels (95.140±2.439%) than pure MSB solution (83.953±1.629%). Conclusion: According to the study's findings, the prepared Menasome could be employed as a viable nanovehicle for MSB dermal delivery, a promising solution for the management of human hyperpigmentation disorders.

Cryo-EM and solid state NMR together provide a more comprehensive structural investigation of protein fibrils.

The tropomyosin 1 isoform I/C C-terminal domain (Tm1-LC) fibril structure is studied jointly with cryogenic electron microscopy (cryo-EM) and solid state nuclear magnetic resonance (NMR). This study demonstrates the complementary nature of these two structural biology techniques. Chemical shift assignments from solid state NMR are used to determine the secondary structure at the level of individual amino acids, which is faithfully seen in cryo-EM reconstructions. Additionally, solid state NMR demonstrates that the region not observed in the reconstructed cryo-EM density is primarily in a highly mobile random coil conformation rather than adopting multiple rigid conformations. Overall, this study illustrates the benefit of investigations combining cryo-EM and solid state NMR to investigate protein fibril structure.

Limitations of the rate-distribution formalism in describing luminescence quenching in the presence of diffusion.

When encountering complex fluorescence decays that deviate from exponentiality, a very appealing approach is to use lifetime or rate constant distributions. These are related by Laplace transform to the sum of exponential functions, stretched exponentials, Becquerel's decay function, and others. However, the limitations of this approach have not been sufficiently discussed in the literature. In particular, the time-independent probability distributions of the rate constants or decay times are occasionally used to describe bimolecular quenching. We show that in such a case, this mathematical formalism has a clear physical interpretation only when the fluorophore and quencher molecules are immobile, as in the solid state. However, such an interpretation is no longer possible once we consider the motion of fluorophores with respect to quenchers. Therefore, for systems in which the relative motion of fluorophores and quenchers cannot be neglected, it is not appropriate to use the time-independent rate or decay time distributions to describe, fit, or rationalize experimental results on fluorescence decay.

Transcription of Customized Circularly Polarized Luminescence from Enantiomeric Metal–Organic Framework to Carbon Dots

AbstractChiral carbon dots (CDs) with circularly polarized luminescence (CPL) are one of the most dynamic areas of modern science. However, the design, preparation, and ambiguity mechanism of solid‐state CPL‐active CDs remains a formidable challenge. Herein, for the first time, CDs with customized chiroptical activities in the solid state, especially CPL, are transcribed from chiral metal–organic framework (CMOFs) via a bottle‐around‐ship strategy. Within these CMOFs⊃CDs assemblies, CDs inherited the chirality of the host CMOFs through host–guest interactions, which is revealed by density functional theory (DFT) simulations and experimental results, and amplified the luminescence dissymmetry factor (glum) by effective artificial chiral light‐harvesting systems. Impressively, CMOFs⊃CDs in pairs generated color‐tunable CPL and white CPL with chromaticity coordinates of (0.32, 0.32). Furthermore, benefiting from excellent processability, as luminescent coatings and 3D printing inks, a white circularly polarized light‐emitting diode, and an extended 3D model “light bulb” featuring white CPL are successfully fabricated, respectively. This strategy paves a new avenue for the synthesis and advanced application of solid‐state CPL‐active CDs‐based materials.

Structural transitions in liquid semiconductor alloys: A molecular dynamics study with a neural network potential.

Liquid-liquid phase transitions hold a unique and profound significance within condensed matter physics. These transitions, while conceptually intriguing, often pose formidable computational challenges. However, recent advances in neural network (NN) potentials offer a promising avenue to effectively address these challenges. In this paper, we delve into the structural transitions of liquid CdTe, CdS, and their alloy systems using molecular dynamics simulations, harnessing the power of an NN potential named LaspNN. Our investigations encompass both pressure and temperature effects. Through our simulations, we uncover three primary liquid structures around melting points that emerge as pressure increases: tetrahedral, rock salt, and close-packed structures, which greatly resemble those of solid states. In the high-temperature regime, we observe the formation of Te chains and S dimers, providing a deeper understanding of the liquid's atomic arrangements. When examining CdSxTe1-x alloys, our findings indicate that a small substitution of S by Te atoms for S-rich alloys (x > 0.5) exhibits a structural transition much different from CdS, while a large substitution of Te by S atoms for Te-rich alloys (x < 0.5) barely exhibits a structural transition similar to CdTe. We construct a schematic diagram for liquid alloys that considers both temperature and pressure, providing a comprehensive overview of the alloy system's behavior. The local aggregation of Te atoms demonstrates a linear relationship with alloy composition x, whereas that of S atoms exhibits a nonlinear one, shedding light on the composition-dependent structural changes.

Enantiopure P-Chiral Secondary Phosphines (P*HRR') from the Catalytic Asymmetric Hydrogenation of P═C Bonds.

We report the first bottleable enantiopure P-chiral secondary phosphines from the rhodium-catalyzed asymmetric hydrogenation of phosphaalkenes. Catalytic asymmetric hydrogenation, a reaction of broad academic and industrial importance for C═C, N═C, and O═C bonds, has not previously been reported for the P═C bond. The hydrogenation of ArP═CR2 (Ar = Mes, m-Xyl and TMOP; R = Ph, 4-C6H4F) affords four unprecedented P-stereogenic secondary phosphines in 76%-90% isolated yields with 91%-97% enantiomeric excess (ee). These isolable P-chiral secondary phosphines are configurationally stable indefinitely in the solid state and show only modest loss in ee when kept in solution for over a month at room temperature.

Dual-State Red-Emitting Zinc-Based MOF Accompanied by Dual-Mode and Dual-State Detection: Color Tonality Visual Mode for the Detection of Tetracycline.

Red-emitting metal-organic frameworks (MOFs) are still mostly based on the use of lanthanides or functionalization with red fluorophores. However, production of transition-metal-based MOFs with red-emitting is scarce. This work reports on the synthesis of a novel dual-state red-emitting Zn-based MOF (denoted as UoZ-7) with the capability to detect target molecules in dual state, in solution, and as solid on paper. UoZ-7 gives strong red emission when excited in the solution and in the solid state with 365 nm ultraviolet (UV) lamp irradiation. Coordination-induced emission is the mechanism for the red emission enhancement in the MOF as a restriction of intramolecular rotation occurred to the ligand within the framework structure. UoZ-7 was successfully used for tetracycline (TC) using dual-mode detection, fluorescence-based ratiometry, and color tonality, in the dual state, in solution, and on the paper. TC molecules adsorb on the red-emitting UoZ-7 surface, and a yellow-greenish color emerges due to aggregation-induced emission between TC and UoZ-7. Concurrently, the inner filter effect diminishes the red emission of UoZ-7. The dual-mode or dual-state detection platform provides a simple and reliable fast method for the detection of TC on-site in various environmental and biomedical applications. Moreover, red-emitting UoZ-7 will have further luminescence-based biomedical applications.

Substituent effects on the mechanochromic behaviour of pyrene-based AIEgens

It is extremely significant and desirable to integrate the fascinating properties of mechanochromism and aggregation-induced emission (AIE) in one simple molecule. Herein, pyrene-based aggregation-induced emission luminogens (AIEgens) with mechanofluorochromic (MFC) properties solve the traditionally existing aggregation-caused quenching (ACQ) challenge. Three cyanoethylene-functionalized pyrene-based derivatives were designed and synthesized. All compounds exhibit remarkable aggregation-enhanced emission (AEE) activity by a 3–20 times enhancement in mixed H2O/THF solutions. More importantly, high fluorescence efficiency was recorded in the solid state, especially for the luminogen 2c, with more than 200 times observed increased efficiency from 0.3% in solution to 69.8% in the solid state. Meanwhile, excellent mechanochromism properties and reversibility against the grinding treatment was systematically investigated. The excellent fatigue resistance properties are a necessity for potential applications in the field of anti-counterfeiting fluorescent inks and for the encryption of security information.

Two-step spin coating approach of hybrid perovskite solid state solar cells: effects of thermal annealing temperatures

Two-step spin coating approach of hybrid perovskite solid state solar cells: effects of thermal annealing temperatures

Phase-field modeling of interdiffusion between dissimilar Fe-Cr-Ni alloys during non-isothermal hot isostatic pressing

Powder metallurgy hot isostatic pressing (PM-HIP) has emerged as a promising alternative to welding for joining dissimilar metals. During HIP, interfacial bonding is mediated by solid state diffusion. The interdiffusion zone across the interface depends on processing conditions, calling for the need for accurate numerical tools capable of simulating interdiffusion and possible phase transformation in order to optimize processing parameters. Here, a phase-field (PF) model based on CALPHAD-based free energy functionals is developed to simulate the interdiffusion and phase evolution between dissimilar Fe–Cr–Ni based steels undergoing HIP and is demonstrated using the interface between 316L and SA508 steels. To overcome the numerical challenges caused by the singular magnetic and entropy terms in the CALPHAD free energy models in the Fe–Cr-Ni system, polynomial functions are fitted with temperature dependent coefficients represented by Fourier series to accurately describe the phase stability of both fcc and bcc phases in the composition and temperature space. This enables simulations of non-isothermal HIP cycles. Diffusivity data from commercial software and literature are taken to parameterize the kinetic parameters. A discrete nucleation model is incorporated for possible phase transformation. The modified thermodynamic models are validated against previous experiments at 923 K and 1273 K. The interdiffusion kinetics are benchmarked against new HIP experiments joining powder and bulk 316L to bulk SA508 with three different HIP cycles. The good agreement between simulations and experiments on both phase stability and interdiffusion indicate that the model is suitable for simulating interdiffusion between Fe–Cr–Ni alloys during HIP cycles. It is also found that using powder and bulk 316L gives similar interdiffusion profiles at elevated temperature when a dense interface forms during HIP.

Highly efficient and thermally stable photonic ceramic by controllable and full crystallization from glass

Polycrystalline ceramics are promising for a diverse range of applications in solid state laser, lighting, scintillator and optical storage. Unfortunately, current ceramic elaborations involves strict and complex synthetic procedures such as ultra-high pressure and vacuum processing. Here, we realize the tune of MgAl2Si4O12 and Mg2Al4Si5O18 phase formation in a glass by controlling the two crystal nucleation and growth individually, and obtain a polycrystalline non-stoichiometric Mg2-x/2Al4-xSi5+xO18:Eu2+ translucent ceramic by virtue of complete and congruent crystallization of the glass. Microstructural characterizations verify that the resulting ceramic exhibits dense and closely stacked micrometer-scale crystallites with very thin grain boundary structure. Chemical composition analysis by energy dispersive X-ray spectrometry revels the grain's composition is highly deviated from the stoichiometric Mg2Al4Si5O18, with atomic ratio Mg/Al/Si of 1.00: 1.46: 2.70. The precipitated non-stoichiometric Mg2-x/2Al4-xSi5+xO18, structurally having infinite channels z = 0.25 or 0.75 sites that run parallel to the c-aix, provides an robust crystal-field environment for Eu2+ 5d-4f transition. As a consequence, the ceramic produces intense emission with photoluminescence quantum yield (PLQY) up to 90 %, and excellent thermal stability emission with 70.1 % emission intensity at 420 K relative to that at room temperature, demonstrating it can be applied in high power lighting application with improved light quality by employing the ceramic as a color converter. Moreover, the ceramic also exhibits thermally stimulated luminescence at temperature reaching up to 700 K, originating from the deep electronic traps in Mg2-x/2Al4-xSi5+xO18 lattice with estimated trap depth of 0.73eV and 0.97eV. We also demonstrate the ceramic is hopeful for optical information storage application as the storage information can be retain well without vulnerable by the fluctuations of external environments due to the deep traps.

Encapsulation of the vanadium substituted Keggin polyoxometalates [α-PVW11O40]4- and [α-PV2W10O40]5- in HKUST-1.

Two POM@MOF hybrid materials composed of a copper-based metal-organic framework (MOF) [Cu3(C9H3O6)2(H2O)3]n (HKUST-1) encapsulating vanadium-substituted Keggin polyoxometalates (POM), [α-PVW11O40]4- (PVW11) and [α-PV2W10O40]5- (PV2W10), were prepared and characterized. PVW11@HKUST-1 and PV2W10@HKUST-1 were synthesized hydrothermally by self-assembly of HKUST-1 in the presence of the preformed POMs, [α-PVW11O40]4- and [α-PV2W10O40]5-, respectively. The two POM@MOF composites were characterized by X-ray diffraction, TGA, BET surface area analysis and FT-IR and Raman spectroscopy. The electronic structure of the POM@MOF materials and their respective constituents is surveyed using solid state UV-vis reflectance spectroscopy. The UV-vis spectra order the oxidizing strength of the POM constituents ([α-PV2W10O40]5- > [α-PVW11O40]4-) and reveal the distinct electronic structure of the POM@MOF materials obtained by synthetic encapsulation of mono- and di-vanadium substituted Keggin polyoxotungstates in HKUST-1.

Atomistic Compositional Details and Their Importance for Spin Qubits in Isotope-Purified Silicon Quantum Wells.

Understanding crystal characteristics down to the atomistic level increasingly emerges as a crucial insight for creating solid state platforms for qubits with reproducible and homogeneous properties. Here, isotope concentration depth profiles in a SiGe/28Si/SiGe heterostructure are analyzed with atom probe tomography (APT) and time-of-flight secondary-ion mass spectrometry down to their respective limits of isotope concentrations and depth resolution. Spin-echo dephasing times and valley energy splittings EVS around have been observed for single spin qubits in this quantum well (QW) heterostructure, pointing toward the suppression of qubit decoherence through hyperfine interaction with crystal host nuclear spins or via scattering between valley states. The concentration of nuclear spin-carrying 29Si is 50 ± 20ppm in the 28Si QW. The resolution limits of APT allow to uncover that both the SiGe/28Si and the 28Si/SiGe interfaces of the QW are shaped by epitaxial growth front segregation signatures on a few monolayer scale. A subsequent thermal treatment, representative of the thermal budget experienced by the heterostructure during qubit device processing, broadens the top SiGe/28Si QW interface by about two monolayers, while the width of the bottom 28Si/SiGe interface remains unchanged. Using a tight-binding model including SiGe alloy disorder, these experimental results suggest that the combination of the slightly thermally broadened top interface and of a minimal Ge concentration of % in the QW, resulting from segregation, is instrumental for the observed large . Minimal Ge additions <1%, which get more likely in thin QWs, will hence support high EVS without compromising coherence times. At the same time, taking thermal treatments during device processing as well as the occurrence of crystal growth characteristics into account seems important for the design of reproducible qubitproperties.

Hydrogen bond crosslinking hydrogel for high-performance ultra-low temperature MXene-based solid state supercapacitors

The electrochemical performance of aqueous electrolytes at low temperatures is frequently suboptimal due to their low freezing point (0 °C). In this study, we constructed MXene-based ultra-low temperature polyvinyl alcohol/nanocellulose-H2SO4 (PVA/CNF-H2SO4) hydrogel electrolytes utilising hydrogen bonding between water molecules and nanocellulose. The process results in a reduction in the amount of free water present in the hydrogel electrolyte, lowering its freezing point to -77.35 °C. PVA/CNF-H2SO4-based solid-state supercapacitors (C7-SSC) demonstrate a capacitance of up to 813 mF cm-2 at -50 °C, exhibiting high-rate performance at low temperatures. The capacitance remains at 45 F g-¹ at a current density of 20 A g-¹. The maximum areal energy and power densities of our C7-SSC achieve 113 μWh cm-² and 0.4 μW cm-² at -50 °C, respectively, surpassing the majority of state-of-the-art devices. This work provides new insights into MXene-based hydrogel manufacturing and expands the range of potential applications for such materials.

Cuprophilic Interactions in Polymeric [Cu10O2(Mes)6]n.

The properties of cuprophilic compounds and the underlying fundamental principles responsible for the Cu(I)···Cu(I) interactions have been the subject of intense research as their diverse structural and physical attributes are being explored. In this light, we performed a new study of the compound [Cu10O2(Mes)6] reported by Haakansson et al. using state of the art experimental and theoretical analysis techniques. Doing this, we found the compound to be a polymer in the solid state, best written as [Cu10O2(Mes)6]n, with unsupported Cu(I)···Cu(I) contacts linking the monomers (2.776 Å). The monomeric unit also exhibits various cuprophilic contacts bridged by mesityl and/or oxo ligands. The compound was analyzed in its solid state, revealing luminescent properties resulting from two distinct fluorescent emissions, as well as in solution, in which its polymeric structure reversibly decomposes. A quantum theory of atoms in molecules (QTAIM) analysis based on density functional theory (DFT) calculations allows to characterize the various Cu(I)···Cu(I) contacts, in which only a few, and not necessarily the shortest, are associated with a bond critical point. Additionally, an energy decomposition analysis of the bonding between monomers indicates that it is dominated by dispersion forces in which the ligands play a dominant role, resulting in bonding energies significantly larger than found in previous DFT investigations based on less bulky models.

Impact of Synthesis Method on the Structure and Function of High Entropy Oxides.

The term sample dependence describes the troublesome tendency of nominally equivalent samples to exhibit different physical properties. High entropy oxides (HEOs) are a class of materials where sample dependence has the potential to be particularly profound due to their inherent chemical complexity. In this work, we prepare a spinel HEO of identical nominal composition by five distinct methods, spanning a range of thermodynamic and kinetic conditions: solid state, high pressure, hydrothermal, molten salt, and combustion syntheses. By structurally characterizing these five samples across all length scales with a variety of X-ray methods, we find that while the average structure is unaltered, the samples vary significantly in their local structures and their microstructures. The most profound differences are observed at intermediate length scales, both in terms of crystallite morphology and cation homogeneity. As revealed by X-ray fluorescence microscopy ideal cation homogeneity is achieved only in the case of combustion synthesis. These structural differences in turn significantly alter the observed functional properties, which we demonstrate via characterization of their magnetic response. While ferrimagnetic order is retained across all five samples, the sharpness of the transition, the size of the saturated moment, and the coercivity all show marked variations with synthesis method. We conclude that the chemical flexibility inherent to HEOs is complemented by strong synthesis method dependence, providing another axis along which to optimize these materials for a wide range of applications.

Energy-efficient and directional preparation of cellulose nanosheets by one-pot surface modification assisted swelling method

The energy-intensive and time-consuming process required for disassembling natural materials into nanoblocks are the major obstacles for the practical applications of biopolymer nanomaterials. Herein, a one-pot, energy-efficient and directional preparation method for gently exfoliating cellulose into nanosheets was achieved by surface modification assisted swelling process. The resulting cellulose nanosheets (CNSs) exhibited diameters ranging from 100 to 480 nm and thicknesses of approximately 5 nm, with a maximum yield of 97.9 %. This method could be widely applicable to common cellulose raw materials. Contrary to other nanocellulose reported previously, CNSs could be dried and stored in solid state, and re-dispersed in aqueous phase, thereby convenient for storage and transportation. Cellulose nanosheets films (CNSFs) obtained from CNSs showed high transparencies (>90 %) and excellent gas barrier properties, especially for the water vapor permeability of only 0.0072×10−10 cm3 cm cm−2 s−1 Pa−1, which were superior to other cellulose based films. In the simulation experiment of dry food packaging, CNSF10 possessed remarkable water vapor and oxygen blocking capabilities comparable to commercial cling films and met the practical requirements. The preparing process of CNSs reported here had the advantages including easy implementation, energy efficiency, and environmentally friendliness, and expanded possibilities for large-scale and widespread utilization of nanocellulose.

Simultaneous Cycloadditions in the Solid State via Supramolecular Assembly.

Chemical reactions conducted in the solid phase (specifically, crystalline) are much less numerous than solution reactions, primarily due to reduced motion, flexibility, and reactivity. The main advantage of crystalline-state transformations is that reactant molecules can be designed to self-assemble into specific spatial arrangements, often leading to high control over product regiochemistry and/or stereochemistry. In crystalline-phase transformations, typically only one type of reaction occurs, and a sacrificial template molecule is frequently used to facilitate self-assembly, similar to a catalyst or enzyme. Here, we demonstrate the first system designed to undergo two chemically unique and orthogonal cycloaddition reactions simultaneously within a single crystalline solid. Well-controlled supramolecular self-assembly of two molecules containing different reactive moieties affords orthogonal reactivity without use of a sacrificial template. Using only UV light, the simultaneous [2+2] and [4+4] cycloadditions are achieved regiospecifically, stereospecifically, and products are obtained in high yield, whereas a simultaneous solution-state reaction affords a mixture of isomers in low yield. Application of dually-reactive systems toward (supra)molecular solar thermal storage materials is also discussed. This work demonstrates fundamental chemical approaches for orthogonal reactivity in the crystalline state and highlights the complexity and reversibility that can be achieved with supramolecular design.

Mechanochemical Polyoxometalate Super-Reduction with Lithium Metal.

In this first systematic investigation of mechanochemical polyoxometalate (POM) reduction, (TBA)3[PMo12O40] was reacted with n equiv of lithium metal (n = 1-24) to generate PMo12/n products which were shown to be mixtures of electron-rich PMo12Lix species. FTIR analysis revealed the lengthening/weakening of terminal Mo═O bonds with increasing levels of reduction, while EXAFS spectra indicated the onset of Mo-Mo bond formation at n ∼ 8 and a significant structural change at n > 12. Successive MoVI reductions were monitored by XANES and XPS, and at n = 24, results were consistent with the formation of at least one MoIV-MoIV bonded {MoIV3} triad together with MoV. Upon dissolution, the PMo12Lix species present in the solid PMo12/n products undergo electron exchange and single-peak 31P NMR spectra were observed for n = 1-12. For n ≥ 16, changes in solid state and solution 31P NMR spectra coincided with the emergence of features in the UV-vis spectra associated with MoV-MoV and {MoIV3} bonding in an ε-Keggin structure. Bonding between {Li(NCMe)}+ and 2-electron-reduced PMo12 in (TBA)4[PMo12O40{Li(NCMe)}] suggests that super-reduction gives rise to more extensive Li-O bonding that ultimately causes lithium-oxide-promoted TBA cation decomposition and POM degradation, which might explain the appearance of XPS peaks for Mo2C at n ≥ 16. This work has revealed some of the complex, unexplored chemistry of super-reduced POMs and establishes a new, solvent-free approach in the search for a better fundamental understanding of the electronic properties and reactivity of electron-rich nanoscale metal oxides.