Molecular Nanoclusters Research Articles

Isomerism in Molecular Metal Carbonyl Clusters

The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

Synthesis, characterization, crystal structures and biological activity of novel NiII2ZnII2 complexes derived from 2-(3-ethoxy-2-hydroxybenzylideneamino)-4-methylphenol

Molecular nanoclusters comprising heterometallic Ni-Zn cores are an interesting class of compounds. In this paper, five novel NiII-ZnII complexes [Ni2Zn2ClL3(HL)3]·0·.25H2O (1), [Ni2Zn2BrL3(HL)3]·0·.25H2O (2), [Ni2Zn2Br2L2(N3)2(MeOH)2]·2MeOH (3), [Ni2Zn2I2L2(N3)2(MeOH)2]·2MeOH (4), and [Ni2Zn2I2L2(N3)2(DMF)2] (5), were prepared from the Schiff base 2-(3-ethoxy-2-hydroxybenzylideneamino)-4-methylphenol (H2L). The complexes have been characterized by elemental analysis, IR, UV–Vis spectra. Molecular structures of the complexes have been determined by single crystal X-ray determination. In complexes 1 and 2, three of the Schiff bases coordinate to the metal atoms via ether oxygen, imino nitrogen and two phenolate oxygen atoms, while the fourth one coordinates through ether oxygen, imino nitrogen and one phenolate oxygen atoms. In complexes 3, 4 and 5, all the donor atoms in the Schiff base ligands participate in coordination. The Ni and Zn atoms in the complexes are in octahedral and trigonal bipyramidal coordination, respectively. The anions of the metal salts and the azide anion, as well as methanol and DMF molecules furnish the coordination sphere. The compounds were evaluated for their antibacterial activities on Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas fluorescens, and antifungal activities on Candida albicans and Aspergillus niger. Interestingly, the complexes have effective activities against Bacillus subtilis and Staphylococcus aureus.

Ultra‐Small Au Nanoclusters with Tailored Photoluminescence Properties using Modified Thiol Ligands: A Computational and Experimental Demonstration

AbstractAu nanoclusters with tailored photoluminescence can be obtained through controlled nanoparticle ligand interface chemistry. The present work reports molecular gold nanoclusters with tuneable photoluminescence emission from 600 to 700 nm using N,N′,N″‐trialkyl (11‐mercaptoundecyl)ammonium chloride ligands as capping‐agents. The tunability within red spectral region is regulated through specific interface chemistry between gold nanoclusters of molecular range and functional groups of the quaternary ammonium head over N,N′,N″‐trialkyl(11‐mercaptoundecyl)ammonium chloride. Combined understanding obtained from the spectroscopy, microscopy, and density functional theory studies demonstrate that the functional group specific electronic interactions at the interfaces steer the emission characteristics of “molecular” Au nanoparticles. The study clearly identifies that bulkier functional groups, i.e., triethyl, tripropyl, tributyl, and dimethyl benzene over N+ (of thiol ligand) through their steric effects minimize the particle size giving rise to tunable photoluminescence emission in red spectral region. However, the red shift seen in the emission Au nanoclusters with N‐(11‐mercaptoundecyl)‐N,N′‐dimethylbenzenammonium chloride ligand in contradiction to particle size effect is computationally proved to be due to the delocalization of electron density from benzene aromatic ring to N+ of ammonium head leading to a reduction in the HOMO‐LUMO energy gap.

Synthesis, characterization, crystal structures and biological activity of 4-chloro-2-(2-hydroxy-3-ethoxybenzylideneamino)phenol and complexes

Molecular nanoclusters comprising a heterometallic 3d-4f stoichiometry are an interesting class of compounds. In this paper, a chloro-containing Schiff base 4-chloro-2-(2-hydroxy-3-ethoxybenzylideneamino)phenol (H2L) was prepared by condensation reaction of 3-ethoxysalicylaldehyde with 2-amino-4-chlorophenol in methanol. The Schiff base is predisposed to chelate within a cluster core both 3d and 4f metal ions. Reaction of H2L with nickel salts afforded a tetranuclear NiII complex [Ni4L4(MeOH)4] (1), while with nickel salts and lanthanide(III) nitrate three tetranuclear NiII-LnIII complexes [Ni2Eu2L4(NO3)2(DMF)2] (2), [Ni2Er2L4(NO3)2(DMF)2] (3), [Ni2Tb2L4(CH3COO)2(DMF)2]·4DMF (4) were obtained. H2L and the complexes have been characterized by elemental analysis, IR, UV–Vis spectra. H2L has also been characterized by 1H and 13C NMR spectra. Molecular structures of the compounds have been determined by single crystal X-ray determination. In the complexes, the Schiff base ligands coordinate to the metal atoms via ether oxygen, imino nitrogen and two phenolate oxygen atoms. All the Ni atoms in the complexes are in octahedral coordination. The rare earth metal atoms are eight coordinated by the phenolate and ether oxygen of the Schiff base ligands, and anionic and solvent oxygen atoms, forming square antiprismatic coordination. The compounds were evaluated for their antibacterial activities on Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas fluorescens, and antifungal activities on Candida albicans and Aspergillus niger, and gave interesting results.

Controlled nanocrystallization of gold nanoclusters within surfactant envelopes: enhancing aggregation-induced emission in solution.

The nanocrystallization of functional molecules has been a subject of recent interest in the current development of nanotechnology. Herein, we report the unprecedented synthesis of single nanocrystals of a molecular gold nanocluster in a homogeneous solution by using surfactant-based nano-envelopes. The co-assembling of a Au8 nanocluster carrying lipophilic phosphine ligands with sodium dodecyl sulfate (SDS) in an aqueous solution results in the formation of sphere-shaped amorphous nano-aggregates coated with the surfactant. Upon sonication, the spherical amorphous aggregates are smoothly shape-shifted into discrete rhombic nanocrystals, which can be tracked by TEM and solution XRD. The transformation into single nanocrystals occurs exclusively without further growth or agglomeration, implying that the crystal growth is restricted within the surfactant nano-envelopes. The robust but flexible nature of the wrapped surfactant is likely responsible for the controlled crystallization. We also demonstrate that the amorphous-to-nanocrystalline transition in solution remarkably enhances the photoluminescence emission from the nanocluster, providing a clear example of crystallization-induced emission enhancement. Notably, the obtained nanocrystals showed high stability in solution and retained their shape, size, and PL intensity even after several months, owing to the densely packed surfactant shell. The present surfactant-directed nanocrystallization method may be applicable to other molecular species to contribute to the development of nanocluster science as well as the designed synthesis of nanomaterials.

Tailoring sensitization properties and improving near-infrared photon upconversion performance through alloying in superatomic molecular Au25 nanoclusters.

Noble-metal nanoclusters (NCs) protected by organic ligands have recently come to the forefront as potent triplet sensitizers for photon upconversion (UC) via triplet-triplet annihilation (TTA), owing to their capacity for atomic-level photophysical property customization. Among these, the rod-shaped bi-icosahedral [Au25(PPh3)10(S-C2H4Ph)5Cl2]2+ (Au-rod) NC is a particularly iconic superatomic molecular NC, recently identified as a near-infrared (NIR)-absorbing sensitizer for TTA-UC. In this study, we synthesized Cu-doped NCs, [Au25-xCux(PPh3)10(S-C2H4Ph)5Cl2]2+ (AuCu-rod), and paired them with 9,10-bis(phenylethynyl)anthracene (BPEA) annihilator/emitter to explore the impact of Cu-doping on the triplet sensitization and NIR-UC performance. The triplet state of AuCu-rod, with lifetime of 3 μs, exhibited a modest blue shift compared to the Au-rod, resulting in the increment in the driving force for triplet energy transfer (TET) to the BPEA acceptor. The TET rate constant was determined to be 5.0 × 107 M-1 s-1, which is an order of magnitude higher than the rate constant for the Au-rod/BPEA pair. This improvement has led to a remarkable increase in the TET efficiency. Notably, the AuCu-rod/BPEA pair facilitated the efficient UC of 805 nm NIR light into 510 nm visible light, realizing a large anti-Stokes shift close to 0.9 eV. The UC internal quantum yield of this combination was determined to be 2.33 ± 0.05%, marking a fivefold enhancement over the Au-rod sensitizer (0.49%). Thus, alloying NC sensitizers offers a promising route to enhance UC performance by tuning the triplet state energy and optimizing the compatibility between the sensitizer and annihilator. Additionally, in this series of experiments, the formation of small amounts of BPEA microaggregates was observed. These aggregates did not undergo singlet fission and could retain multiple long-lived triplet excitons. This characteristic facilitated TTA among triplet excitons, resulting in efficient NIR-to-visible UC emission.

C60 fullerene nanoparticles permeability through the model lipid envelope of coronavirus and their anticoronavirus effect in the in ovo system

Background: An urgent problem of modern biomedicine is the search for potential ways to reduce the spread of coronavirus infections in human and animal populations and eliminate the impact of coronavirus on their bodies. Aim of the work was to determine the structural organization of C60 fullerenes in a model cell medium, to assess their potential ability to penetrate the model lipid envelope of a coronavirus, thus destroying its integrity, as well as the effectiveness of the anticoronavirus action in the in ovo system. Methods: The research was conducted using the Gromacs 2020 software package and the Charmm36 force field. The CHARMM-GUI web resource was used to construct the lipid envelope of a coronavirus. Virological and toxicological methods were used in the in ovo experiments. Results: It is shown that at the initial stages of molecular dynamics C60 fullerene forms small nanoclusters in the amount of 7–16 molecules, which is affected by the initial concentration of C60 fullerene in a model cell medium. At the same time, the shape of nanostructures for the number of molecules over 16 may differ from the correct spherical shape. It was established that C60 fullerene and its nanoclusters are able to penetrate inside the lipid envelope of a coronavirus. In particular, a single C60 molecule can migrate, completely embed itself in the lipid envelope, or move within it. It was found that C60 fullerene aqueous solution, at the maximum permissible concentration (MPC) of 30 μg/embryo, reduces the infectious activity of the chicken infectious bronchitis (CIB) coronavirus when it is used 1, 2 and 4 h after the infection of a sensitive biological system with a coronavirus. Conclusions: It is shown that aggregation of C60 fullerene in a model cell medium can occur in different ways: either before penetration into the lipid envelope of a coronavirus, or inside it. C60 fullerenes, both individually and as part of nanoclusters, are able to form pores in the envelope of a coronavirus, destroying its integrity, which possibly leads to disruption of the corresponding stages of its replication cycle and attachment to cell receptors. It was established that C60 fullerene aqueous solution, when used in the MPC value, shows antiviral activity against the CIB coronavirus in its early stages of interaction with the cell (1–4 h).

Quantifying plasmonic characteristics of pure and alkali doped aluminium clusters

Study of plasmonic response of molecules and metal nanoclusters have drawn a considerable attention during recent times due to their various practical applications. In this study, the optical properties and the plasmonic response of our recently reported Al13+ cluster [Guin et al. Journal of Molecular Graphics and Modelling, 2020, 97, 107544] and its alkali doped counterparts [Guin et al. Journal of Molecular Modeling, 2021, 27, 235] have been investigated based on Transition dipole moment (TDM), Natural Transition Orbital (NTO) and transition inverse participation ratio (TIPR) indices. Recently these indices have been utilized by various scientists to characterize plasmonic transitions of molecular systems and metal nanoclusters. In TDM analysis, the magnitude of all the contributing TDMs associated with the molecular orbital transitions have been estimated along with the angles the individual dipoles make with the resultant dipole moment vector. A transition having at least two dominating TDM contributions along with phase matching indicate a collective or plasmonic transition. The collectiveness of orbital transitions is also corroborated through NTO and TIPR analysis. The effect of solvent medium on the optical properties and plasmonic transitions have also been studied using time dependent density functional theory in the conductor like polarizable continuum model (TDDFT-CPCM). The solvent has a strong impact on the optical properties as well as the plasmonic response of the clusters. The dielectric environment of the solvent red shifts and broadens the spectra with respect to that in the gas phase. Plasmon like excitations have been found for Li doped Al13+ cluster without solvent and Na doped Al13+ cluster in ethanol and THF.

Multi-Time-Scale Simulation of Complex Reactive Mixtures: How Do Polyoxometalates Form?

Understanding the dynamics of reactive mixtures still challenges both experiments and theory. A relevant example can be found in the chemistry of molecular metal-oxide nanoclusters, also known as polyoxometalates. The high number of species potentially involved, the interconnectivity of the reaction network, and the precise control of the pH and concentrations needed in the synthesis of such species make the theoretical/computational treatment of such processes cumbersome. This work addresses this issue relying on a unique combination of recently developed computational methods that tackle the construction, kinetic simulation, and analysis of complex chemical reaction networks. By using the Bell-Evans-Polanyi approximation for estimating activation energies, and an accurate and robust linear scaling for correcting the computed pKa values, we report herein multi-time-scale kinetic simulations for the self-assembly processes of polyoxotungstates that comprise 22 orders of magnitude, from tens of femtoseconds to months of reaction time. This very large time span was required to reproduce very fast processes such as the acid/base equilibria (at 10-12 s), relatively slow reactions such as the formation of key clusters such as the metatungstate (at 103 s), and the very slow assembly of the decatungstate (at 106 s). Analysis of the kinetic data and of the reaction network topology shed light onto the details of the main reaction mechanisms, which explains the origin of kinetic and thermodynamic control followed by the reaction. Simulations at alkaline pH fully reproduce experimental evidence since clusters do not form under those conditions.

High dispersion Pd nanoclusters modified sulfur-rich vacancies ZnIn2S4 for high-performance hydrogen evolution

Hydrogen energy is regarded as the clean energy alternative for fossil energy. Hydrogen evolution reaction (HER) is a sustainable way for the production of hydrogen energy. However, commercial platinum (Pt) catalysts for HER are expensive and scarce, which will not fully meet the demand of the future market. Therefore, scientists have been actively exploring alternatives to Pt-based catalysts. Studies have shown that palladium (Pd) and Pt have similar catalytic activity in HER. Small molecular Pd nanoclusters can be used as a perfect HER activity center. Herein, anchoring of Pd nanoclusters (Pd NCs) on sulfur-vacancy-enriched ZnIn2S4 nanosheets (Pd/ZIS-T) has been successfully achieved. The zeta potential value for ZnIn2S4 is −59.9 mV, indicating that the surface of ZnIn2S4 is abundant negatively charged in deionized water, thus providing plentiful anchoring sites to absorb Pd2+. The results show that the synergistic effect of Pd NCs and sulfur vacancies will endow the obtained catalyst with excellent electrocatalytic activity and stability. It also managed to reducing costs by reducing noble metal content. In particular, the Pd/ZIS-T electrocatalyst with excellent performance delivered low overpotential of 25 mV at 10 mA cm−2 and small Tafel slope of 33 mV dec-1 in acidic electrolyte.

From Au11 to Au13: Tailored Synthesis of Superatomic Di-NHC/PPh3-Stabilized Molecular Gold Nanoclusters

Herein, we report a new method to synthesize molecular gold nanoclusters (AuNCs) stabilized by phosphine (PR3) and di-N-heterocyclic carbene (di-NHC) ligands. The interaction of di-NHC gold(I) complexes, with the general formula [(di-NHC)Au2Cl2] with well-known [Au11(PPh3)8Cl2]Cl clusters provides three new classes of AuNCs through a controllable reaction sequence. The synthesis involves an initial ligand metathesis reaction to produce [Au11(di-NHC)(PPh3)6Cl2]+ (type 1 clusters), followed by a thermally induced rearrangement/metal complex addition with the formation of Au13 clusters [Au13(di-NHC)2(PPh3)4Cl4]+ (type 2 clusters). Finally, an additional metathesis process yields [Au13(di-NHC)3(PPh3)3Cl3]2+ (type 3 clusters). The electronic and steric properties of the employed di-NHC ligand affect the product distribution, leading to the isolation and full characterization of different clusters as the main product. A type 3 cluster has been also structurally characterized and was preliminarily found to be strongly emissive in solution.

Ultrasmall PtAu2 nanoclusters activate endogenous anti-inflammatory and anti-oxidative systems to prevent inflammatory osteolysis.

Rationale: Inflammatory osteolysis, characterized by abundant immune cell infiltration and osteoclast (OC) formation, is a common complication induced by bacterial products and/or wear particles at the bone-prosthesis interface that severely reduces long-term stability after implantation. Molecular nanoclusters are ultrasmall particles with unique physicochemical and biological properties that have great potential as theranostic agents for treating inflammatory diseases. Methods: In this study, heterometallic PtAu2 nanoclusters with sensitive nitric oxide-responsive phosphorescence turn-on characteristics and strong binding interactions with cysteine were designed, making them desirable candidates for the treatment of inflammatory osteolysis. Results: PtAu2 clusters exhibited satisfactory biocompatibility and cellular uptake behavior, with potent anti-inflammatory and anti-OC activities in vitro. In addition, PtAu2 clusters alleviated lipopolysaccharide-induced calvarial osteolysis in vivo and activated nuclear factor erythroid 2-related factor 2 (Nrf2) expression by disrupting its association with Kelch-like ECH-associated protein 1 (Keap1), thereby upregulating the expression of endogenous anti-inflammatory and anti-oxidative products. Conclusion: Through the rational design of novel heterometallic nanoclusters that activate the endogenous anti-inflammatory system, this study provides new insights into the development of multifunctional molecular therapeutic agents for inflammatory osteolysis and other inflammatory diseases.

From M6 to M12, M19 and M38 molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters.

Heterometallic Chini-type clusters [Pt6-xNix(CO)12]2- (x = 0-6) were obtained by reactions of [Pt6(CO)12]2- with Ni-clusters such as [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, or from [Pt9(CO)18]2- and [Ni6(CO)12]2-. The Pt/Ni composition of [Pt6-xNix(CO)12]2- (x = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt9(CO)18]2- with [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, as well as reactions of [Pt12(CO)24]2- with [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, afforded [Pt9-xNix(CO)18]2- (x = 0-9) species. [Pt6-xNix(CO)12]2- (x = 1-5) were converted into [Pt12-xNix(CO)21]4- (x = 2-10) upon heating in CH3CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt12-xNix(CO)21]4- (x ≈ 8) with HBF4·Et2O afforded the [HPt14+xNi24-x(CO)44]5- (x ≈ 0.7) nanocluster. Finally, [Pt19-xNix(CO)22]4- (x = 2-6) could be obtained by heating [Pt9-xNix(CO)18]2- (x = 1-3) in CH3CN at 80 °C, or [Pt6-xNix(CO)12]2- (2-4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt19-xNix(CO)22]4- (x = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt19(CO)22]4-.

Phosphorescent Metal Halide Nanoclusters for Tunable Photodynamic Therapy.

Photodynamic therapy (PDT) is currently limited by the inability of photosensitizers (PSs) to enter cancer cells and generate sufficient reactive oxygen species. Utilizing phosphorescent triplet states of novel PSs to generate singlet oxygen offers exciting possibilities for PDT. Here, we report phosphorescent octahedral molybdenum (Mo)-based nanoclusters (NC) with tunable toxicity for PDT of cancer cells without use of rare or toxic elements. Upon irradiation with blue light, these molecules are excited to their singlet state and then undergo intersystem crossing to their triplet state. These NCs display surprising tunability between their cellular cytotoxicity and phototoxicity by modulating the apical halide ligand with a series of short chain fatty acids from trifluoroacetate to heptafluorobutyrate. The NCs are effective in PDT against breast, skin, pancreas, and colon cancer cells as well as their highly metastatic derivatives, demonstrating the robustness of these NCs in treating a wide variety of aggressive cancer cells. Furthermore, these NCs are internalized by cancer cells, remain in the lysosome, and can be modulated by the apical ligand to produce singlet oxygen. Thus, (Mo)-based nanoclusters are an excellent platform for optimizing PSs. Our results highlight the profound impact of molecular nanocluster chemistry in PDT applications.

Supramolecular Anchoring of Polyoxometalate Amphiphiles into Nafion Nanophases for Enhanced Proton Conduction.

Advanced proton exchange membranes (PEMs) are highly desirable in emerging sustainable energy technology. However, the further improvement of commercial perfluorosulfonic acid PEMs represented by Nafion is hindered by the lack of precise modification strategy due to their chemical inertness and low compatibility. Here, we report the robust assembly of polyethylene glycol grafted polyoxometalate amphiphile (GSiW11) into the ionic nanophases of Nafion, which largely enhances the comprehensive performance of Nafion. GSiW11 can coassemble with Nafion through multiple supramolecular interactions and realize a stable immobilization. The incorporation of GSiW11 can increase the whole proton content in the system and induce the hydrated ionic nanophase to form a wide channel for proton transport; meanwhile, GSiW11 can reinforce the Nafion ionic nanophase by noncovalent cross-linking. Based on these synergistic effects, the hybrid PEMs show multiple enhancements in proton conductivity, tensile strength, and fuel cell power density, which are all superior to the pristine Nafion. This work demonstrates the intriguing advantage of molecular nanoclusters as supramolecular enhancers to develop high-performance electrolyte materials.

Arsenic Monolayers Formed by Zero-Dimensional Tetrahedral Clusters and One-Dimensional Armchair Nanochains.

One-dimensional (1D) arsenene nanostructures are predicted to host a variety of interesting physical properties including antiferromagnetic, semiconductor-semimetal transition and quantum spin Hall effect, which thus holds great promise for next-generation electronic and spintronic devices. Herein, we devised a surface template strategy in a combination with surface-catalyzed decomposition of molecular As4 cluster toward the synthesis of the superlattice of ultranarrow armchair arsenic nanochains in a large domain on Au(111). In the low annealing temperature window, zero-dimensional As4 nanoclusters are assembled into continuous films through intermolecular van der Waals and molecule-substrate interactions. At the elevated temperature, the subsequent surface-assisted decomposition of molecular As4 nanoclusters leads to the formation of a periodic array of 1D armchair arsenic nanochains that form a (2 × 3) superstructure on the Au(111) surface. These ultranarrow armchair arsenic nanochains are predicted to have a small bandgap of ∼0.50 eV, in contrast to metallic zigzag chains. In addition, the Au-supported arsenic nanochains can be flipped to form a bilayer structure through tip indentation and manipulation, suggesting the possible transfer of these nanochains from the substrate. The successful realization of arsenic nanostructures is expected to advance low-dimensional physics and infrared optoelectronic nanodevices.

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt27(CO)31]4- Displaying a Defective Structure.

The molecular Pt nanocluster [Pt27(CO)31]4– (14–) was obtained by thermal decomposition of [Pt15(CO)30]2– in tetrahydrofuran under a H2 atmosphere. The reaction of 14– with increasing amounts of HBF4·Et2O afforded the previously reported [Pt26(CO)32]2– (32–) and [Pt26(CO)32]− (3–). The new nanocluster 14– was characterized by IR and UV–visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy. The cluster displays a cubic-close-packed Pt27 framework generated by the overlapping of four ABCA layers, composed of 3, 7, 11, and 6 atoms, respectively, that encapsulates a fully interstitial Pt4 tetrahedron. One Pt atom is missing within layer 3, and this defect (vacancy) generates local deformations within layers 2 and 3. These local deformations tend to repair the defect (missing atom) and increase the number of Pt–Pt bonding contacts, minimizing the total energy. The cluster 14– is perfectly diamagnetic and displays a rich electrochemical behavior. Indeed, six different oxidation states have been characterized by IR SEC, unraveling the series of 1n– (n = 3–8) isostructural nanoclusters. Computational studies have been carried out to further support the interpretation of the experimental data.

Ligand engineering of Au nanoclusters with multifunctional metalloporphyrins for photocatalytic H2O2production

A molecular Au nanocluster (NC)-based photocatalyst was developed by chemically grafting the three-in-one function of Co-TCPP molecules for improved photocatalytic H2O2production.

Atomically Precise Ni-Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy.

The molecular nanocluster [Ni36–xPd5+x(CO)46]6– (x = 0.41) (16–) was obtained from the reaction of [NMe3(CH2Ph)]2[Ni6(CO)12] with 0.8 molar equivalent of [Pd(CH3CN)4][BF4]2 in tetrahydrofuran (thf). In contrast, [Ni37–xPd7+x(CO)48]6– (x = 0.69) (26–) and [HNi37–xPd7+x(CO)48]5– (x = 0.53) (35–) were obtained from the reactions of [NBu4]2[Ni6(CO)12] with 0.9–1.0 molar equivalent of [Pd(CH3CN)4][BF4]2 in thf. After workup, 35– was extracted in acetone, whereas 26– was soluble in CH3CN. The total structures of 16–, 26–, and 35– were determined with atomic precision by single-crystal X-ray diffraction. Their metal cores adopted cubic close packed structures and displayed both substitutional and compositional disorder, in light of the fact that some positions could be occupied by either Ni or Pd. The redox behavior of these new Ni–Pd molecular alloy nanoclusters was investigated by cyclic voltammetry and in situ infrared spectroelectrochemistry. All three compounds 16–, 26–, and 35– displayed several reversible redox processes and behaved as electron sinks and molecular nanocapacitors. Moreover, to gain insight into the factors that affect the current–potential profiles, cyclic voltammograms were recorded at both Pt and glassy carbon working electrodes and electrochemical impedance spectroscopy experiments performed for the first time on molecular carbonyl nanoclusters.

Molecular Gold Nanocluster Au156 Showing Metallic Electron Dynamics.

The boundary between molecular and metallic gold nanoclusters is of special interest. The difficulty in obtaining atomically precise nanoclusters larger than 2 nm limits the determination of such a boundary. The synthesis and total structural determination of the largest all-alkynyl-protected gold nanocluster (Ph4P)6[Au156(C≡CR)60] (R = 4-CF3C6H4-) (Au156) are reported. It presents an ideal platform for studying the relationship between the structure and the metallic nature. Au156 has a rod shape with the length and width of the kernel being 2.38 and 2.04 nm, respectively. The cluster contains a concentric Au126 core structure (Au46@Au50@Au30) protected by 30 linear RC≡C-Au-C≡CR staple motifs. It is interesting that Au156 displays multiple excitonic peaks in the steady-state absorption spectrum (molecular) and pump-power-dependent excited-state dynamics as revealed in the transient absorption spectrum (metallic), which indicates that Au156 is a critical crossover cluster for the transition from molecular to metallic state. Au156 is the smallest-sized gold nanocluster showing metal-like electron dynamics, and it is recognized that the cluster shape is one of the important factors determining the molecular or metallic nature of a gold nanocluster.