[Ba4@Sn56]36- as a Main-Group Second-Order Superatom. Interpenetrated Dodecahedrons as a Three-Dimensional Cluster-of-Clusters Structure.

Superatomic clusters are relevant species to further understanding of bonding and structural properties of atomically precise molecular nanoparticles. Here, we explore the characteristics of ligand-free [Ba4@Sn56]36- Zintl-ion, as a three-dimensional aggregate of clusters featuring four fused Ba@Sn19 building units as an extension of the understanding in linear and cyclic superatomic cluster arrays. We provide a rational picture of the electronic shell in [Ba4@Sn56]36- as a cluster-of-clusters motif through the recently introduced second-order superatom approach, as a three-dimensional aggregation of superatomic clusters where their shells are able to interact. The electronic structure features both tangential and radial shells from the four building Ba@Sn19 units, leading to a set of 1S'21P'61D'101F'14 and higher angular momentum shells and a second set of 2S'22P'62D'102F'142G'8 second-order shells. Thus, the current approach serves to encourage the rationalization of molecular materials conceived from cluster building blocks toward a rational guide for synthetic efforts.

[K2(Bi@Pd12@Bi20)]4-: An Endohedral Inorganic Fullerene with Spherical Aromaticity.

Inorganic fullerene clusters have attracted widespread attention due to their highly symmetrical geometric structures and intrinsic electronic properties. However, cage-like clusters composed of heavy metal elements with high symmetry are rarely reported, and their synthesis is also highly challenging. In this study, we present the synthesis of a [K2(Bi@Pd12@Bi20)]4- cluster that incorporates a {Bi20} cage with pseudo-Ih symmetry, making it the largest main group metal cluster compound composed of the bismuth element to date. Magnetic characterization and theoretical calculations suggest that the spin state of the overall cluster is a quartet. Quantum chemical calculations reveal that the [Bi20]3- cluster has a similar electronic configuration to C606- and the [Bi@Pd12@Bi20]6- cluster exhibits a unique open-shell aromatic character.

Coinage Metal Complexes of a Sterically Encumbered Anionic Pyridylborate.

Sterically loaded, anionic pyridine has been synthesized and utilized successfully in the stabilization of a homoleptic series of coinage metal complexes.  The treatment of [4-(Ph3B)-2,6-Trip2Py]K (Trip =2,4,6-iPr3C6H2) with CuBr(PPh3), AgCl(PPh3) or AuCl(PPh3) (Py = pyridine) afforded the corresponding [4-(Ph3B)-2,6-Trip2Py]M(PPh3) (M = Au, Ag, Cu) complexes, via salt metathesis, as isolable, crystalline solids.  Notably, these reactions avoid the facile single electron transfer chemistry reported with the less bulky ligand systems.  The X-ray structures revealed that they are two-coordinate metal adducts.  The M-N and M-P bond distances are longest in the silver and shortest in the copper adduct among the three group 11 family members.  Computational analysis revealed an interesting stability dependence on steric bulk of the anionic pyridine (i.e., pyridyl borate) ligand.  A comparison of structures and bonding of [4-(Ph3B)-2,6-Trip2Py]Au(PPh3) to pyridine and m-terphenyl complexes, {[2,6-Trip2Py]Au(PPh3)}[SbF6] and [2,6-Trip2Ph]Au(PPh3) are also provided.  The Au(I) isocyanide complex, [4-(Ph3B)-2,6-Trip2Py]Au(CNBut) has been stabilized using the same anionic pyridylborate illustrating that it can support other gold-ligand moieties as well.

Ligand-free supermolecules: [Pd2@Ge18]4- and [Pd2@Sn18]4- as multiple-bonded Zintl-ion clusters based on Pd@Ge9 and Pd@Sn9 assembled units.

Understanding intercluster bonding interactions is important in the rational synthesis of building blocks for molecular materials. Such characteristics have been developed for coinage metal clusters resembling single-, double-, and triple-bonded species, coined as supermolecules. Herein, we extend such an approach for understanding main-group clusters, thus evaluating [Pd2@E18]4- clusters (E = Ge, Sn) involving the fusion of parent spherical aromatic [Pd@E12]2- building units. Our results indicate intercluster bonding provided by contribution from 2P and 1G shells centered at each building motif, leading to an overall bond order of 2.70 and 2.31 for [Pd2@Ge18]4- and [Pd2@Sn18]4-, respectively. In addition, 119Sn-NMR patterns were evaluated to complement the experimental characterization of a single peak owing to the insolution fluxional behavior of [Pd2@Sn18]4- as three peaks owing to the three sets of unique Sn atoms within the structure. Magnetic response properties revealed that spherical aromatic characteristics from parent [Pd@E12]2- building units are retained in the overall [Pd2@E18]4- oblate cluster as two spherical aromatic units. Hence, the notion of superatomic molecules is extended to Zintl-ion clusters, favoring further rationalization for the fabrication of cluster-assembled solids.

In situ studies of reversible solid-gas reactions of ethylene responsive silver pyrazolates.

Solid-gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF3)3Pz]Ag}3 and {[4-Br-3,5-(CF3)2Pz]Ag}3 supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF3)2Pz]Ag}3 under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above. Complete structural data of three novel silver-ethylene complexes are presented together with a thorough computational analysis of the mechanism.

[Ag(Sn9-Sn9)]5- and [(η4-Sn9)Ag(η1-Sn9)]7-, as aggregates of spherical aromatic building blocks. Persistence of aromaticity upon cluster gathering.

Formation of cluster-based materials requires a fundamental understanding of the resulting cluster aggregation processes. The Sn94- Zintl-ion structure can be viewed as a building block featuring a spherical aromatic species, leading to a cluster gathering upon oxidative coupling and/or mediated by transition metals. Here, we evaluate the spherical aromatic properties of [Sn9-Sn9]6-, [Ag(Sn9-Sn9)]5- and [(η4-Sn9)Ag(η1-Sn9)]7-, as aggregates of two Sn9 building units held together via oxidative coupling and mediated by a Ag(I) transition metal center. Our results from magnetic criteria of aromaticity show that the inherent spherical aromatic characteristics of the parent Sn94- cluster are persistent in the overall aggregate where the enabled shielding cones ascribed to each Sn9 unit are able to interplay between them, leading to an overlap of the shielding regions. Hence, the two approaches for bringing cluster units together are able to retain the inherent spherical aromatic features for each Sn9 unit, leading to a cluster-based dimer where the parent properties remain. Thus, further cluster-based materials can be envisaged from aggregation upon oxidative coupling and/or mediated by transition metals, where the constituent building blocks retain their initial features, useful to guide the formation of more complex cluster-based aggregates.

Correction: When SF5 outplays CF3: effects of pentafluorosulfanyl decorated scorpionates on copper.

[This corrects the article DOI: 10.1039/D1SC04846E.].

Classical Gold Carbonyl Complexes in Tetrahedral and Trigonal-Planar Settings.

A unique four-coordinate, classical gold(I)-carbonyl complex with substantial backdonation from gold has been isolated by using a B-methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage-metal family. The B-arylated ligand version also afforded a gold-carbon monoxide complex that displays a notably low C-O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the AuI -CO bonds of these tris(pyridyl)borate ligand-supported molecules consist of electrostatic attraction, OC→Au σ-donation, and very significant Au→CO π-back-bonding components. The latter is responsible for the observed C-O stretching frequencies, which are lower than in free CO.

Second-order superatoms: Au52-PAP featuring a three-dimensional cluster-of-clusters core.

The recent characterization of Au52-PAP cluster can be viewed as a three-dimensional arrangement featuring four Au13 motifs. As a result, a new set of superatomic orbitals are built up from the superatomic shell of each constituent unit, denoted by 1S'21P'62S'21D'102P'61F'6 and, thus, referred to as a second-order superatomic shell structure. This favors the rationalization of larger species toward the formation of cluster-assembled materials of different sizes.

An all-metal fullerene: [K@Au12Sb20]5.

The C60 fullerene molecule has attracted tremendous interest for its distinctive nearly spherical structure. By contrast, all-metal counterparts have been elusive: Fullerene-like clusters composed of noncarbon elements typically suffer from instability, resulting in more compact geometries that require multiple embedded atoms or external ligands for stabilization. In this work, we present the synthesis of an all-metal fullerene cluster, [K@Au12Sb20]5-, using a wet-chemistry method. The cluster's structure was determined by single crystal x-ray diffraction, which revealed a fullerene framework consisting of 20 antimony atoms. Theoretical calculations further indicate that this distinct cluster exhibits aromatic behavior.

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues.

Thallium(I) complexes of B-methylated and B-phenylated tris(pyridyl)borates featuring trifluoromethyl groups at the pyridyl ring 6-positions have been synthesized by metathesis using the corresponding potassium salts [MeB(6-(CF3)Py)3]K and [PhB(6-(CF3)Py)3]K with thallium(I) acetate. The closely related tris(pyrazolyl)borate analogue [PhB(3-(CF3)Pz)3]Tl has also been prepared, and comparisons of structural and spectroscopic features between the two scorpionate families are presented. [MeB(6-(CF3)Py)3]Tl displays κ3-coordination of the tris(pyridyl)borate similar to that of tris(pyrazolyl)borate in [MeB(3-(CF3)Pz)3]Tl, while [PhB(6-(CF3)Py)3]Tl and [PhB(3-(CF3)Pz)3]Tl feature κ2-N,N ligand coordination modes with the B-phenyl groups flanking the thallium sites. 19F NMR spectroscopy of [MeB(6-(CF3)Py)3]Tl reveals the presence of a remarkably large 1208 Hz four-bond thallium-fluorine coupling constant in chloroform at room temperature, which is considerably larger than 878 Hz observed for the pyrazolyl borate analogue [MeB(3-(CF3)Pz)3]Tl. Although [PhB(6-(CF3)Py)3]Tl is structurally nonrigid at room temperature in chloroform, at lower temperatures, the ligand arm exchange slows down, revealing 4JTl-F = 1110 Hz. Steric demands of these ligands have been quantified using the buried volume concept. In addition, ligand transfer chemistry from [MeB(6-(CF3)Py)3]Tl and [PhB(6-(CF3)Py)3]Tl to copper(I) under ethylene and computational analyses of the various coordination modes of tris(pyrazolyl)borates and tris(pyridyl)borates are reported.

On the structure and electronic properties of Ptn clusters: new most stable structures for n = 16-17.

The lowest energy structures and electronic properties of Ptn clusters up to n = 17 are investigated by using a genetic algorithm in combination with density functional theory calculations. There are several putative global minimum structures for platinum clusters which have been reported by using different approaches, but a comprehensive study for n = 15-17 has not been carried out so far. Herein, we perform a consensus using GGA (PBE), meta-GGA (TPSS) and hybrid (B3PW91, PBE0, PBEh-3c, M06-L) functionals in conjunction with the Def2-TZVP basis set. New most stable structures are found for Pt16 and Pt17, which are slightly lower in energy than the previously reported global minima. Molecular dynamics simulations show that the clusters are rigid at room temperature. We analyze the structural, electronic, energy and vibrational data of the investigated clusters in detail.

Filling the gap with a bulky diaryl boron group: fluorinated and non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety on the backbone.

Successful synthesis has been reported of 4-Mes2B-3,5-(CF3)2PzH and 4-Mes2B-3,5-(CF3)2PzH bearing sterically demanding diarylboron moieties at the pyrazole ring 4-position, and their corresponding copper(I) pyrazolate complexes. They show visible blue photoluminescence in solution. The X-ray crystal structures revealed that the fluorinated {[4-BMes2-3,5-(CF3)2Pz]Cu}3 crystallizes as discrete trinuclear molecules whereas as the non-fluorinated {[4-BMes2-3,5-(CH3)2Pz]Cu}3 forms dimers of trimers with two close inter-trimer Cu⋯Cu separations. The solid {[4-BMes2-3,5-(CF3)2Pz]Cu}3 featuring a sterically confined Cu3N6 core displays bright blue phosphorescence while {[4-BMes2-3,5-(CH3)2Pz]Cu}3, which is a dimer of a trimer, is a red phosphor at room temperature. This work illustrates the modulation of photo-physical properties of metal pyrazolates by adjusting the supporting ligand steric features and introducing secondary diarylboron luminophores. Computational analysis of the structures and photophysical properties of copper complexes are also presented.

Antifungal activity of Co(II) and Cu(II) complexes containing 1,3-bis(benzotriazol-1-yl)-propan-2-ol on the growth and virulence traits of fluconazole-resistant Candida species: synthesis, DFT calculations, and biological activity.

Relevant virulence traits in Candida spp. are associated with dimorphic change and biofilm formation, which became an important target to reduce antifungal resistance. In this work, Co(II) complexes containing a benzotriazole derivative ligand showed a promising capacity of reducing these virulence traits. These complexes exhibited higher antifungal activities than the free ligands against all the Candida albicans and non-albicans strains tested, where compounds 2 and 4 showed minimum inhibitory concentration values between 15.62 and 125 µg mL-1. Moreover, four complexes (2-5) of Co(II) and Cu(II) with benzotriazole ligand were synthesized. These compounds were obtained as air-stable solids and characterized by melting point, thermogravimetric analysis, infrared, Raman and ultraviolet/visible spectroscopy. The analysis of the characterization data allowed us to identify that all the complexes had 1:1 (M:L) stoichiometries. Additionally, Density Functional Theory calculations were carried out for 2 and 3 to propose a probable geometry of both compounds. The conformer Da of 2 was the most stable conformer according to the Energy Decomposition Analysis; while the conformers of 3 have a fluxional behavior in this analysis that did not allow us to determine the most probable conformer. These results provide an important platform for the design of new compounds with antifungal activities and the capacity to attack other target of relevance to reduce antimicrobial resistance.

The use of molecular electronic structure methods to investigate mechanically interlocked molecules.

Mechanically interlocked molecules (MIMs) show several applications as molecular machines, catalysts, and appear as potential structures for ion recognition. Importantly, the understanding of the nature of the mechanical bonds that support the interaction between the non-interlocked components of MIMs is still a poorly explored topic in the literature. Important discoveries in the field of MIMs have been made using molecular mechanics (MM) and, in particular, molecular dynamics (MD) methods. However, obtaining more accurate geometric and energetic parameters requires the use of molecular electronic structure methods. The present perspective highlights some studies of MIMs using density functional theory (DFT) or ab initio electron correlation methods. We expect that the studies highlighted here will show that such large structures can be studied with more precise approaches by selecting the model system to be studied by chemical intuition or supported by low scaling quantum mechanics methods. This will contribute to the elucidation of important properties to be used in the design of various materials.

Charge delocalization and aromaticity of doubly reduced double-walled carbon nanohoops.

Cycloparaphenylenes (CPPs) exhibit selective host capabilities, featuring the ability to incorporate smaller CPPs to form double-walled host-guest complexes. Moreover, CPPs can also be stabilized by global aromaticity under twofold oxidation or reduction, involving electronic conjugation along with the overall structural backbone. Herein we explore the structural modifications, bonding, electron delocalization and magnetic properties of doubly reduced double-walled CPP complexes with DFT methods, in the isolated and aggregate [n + 5]CPP⊃[n]CPP2- (n = 5-8) species. Our results show that the hosts undergo structural, bonding and delocalization deformations towards quinoidal configurations and exhibit global long-ranged shielding cones similar to global aromatic free dianionic CPPs, accounting for charge delocalization on the outer nanohoops, whereas the guests preserve local aromatic benzenoid configurations, resulting in global and local aromatic circuits within the host-guest aggregate. This observation suggests that in multi-layered related species electronic delocalization will be retained at the outer structural surface. The aromaticity of the hosts is manifested in the strong upfield shifts of the guests 1H-NMR signals. Hence, CPP complexes can be extended to doubly reduced species stabilized by global host aromaticity expanding our understanding of doubled-walled nanotubes at the nanoscale regime.

Cl@Si20X20 cages: evaluation of encapsulation nature, structural rigidity, and 29Si-NMR patterns using relativistic DFT calculations.

The experimental characterization of Cl@Si20 endohedral clusters, featuring different ligands such as [Cl@Si20H20]- (1) [Cl@Si20H12Cl8]- (2), and [Cl@Si20Cl20]- (3), provides insight into the variable encapsulation environment for chloride anions. The favorable formation of such species enables the evaluation of the encapsulation nature and the role of the inner anion in the rigidity of the overall cluster. Our results show a sizable interaction which increases as -66.7, -100.8, and -130.3 kcal mol-1 from 1 to 3, respectively, featuring electrostatic character. The orbital interaction involves 3p-Cl → Si20X20 and 3s-Cl → Si20X20 charge transfer channels and a slight contribution from London dispersion-type interactions. These results show that the inner bonding environment can be modified by the choice of exobonded ligands. Moreover, 29Si-NMR parameters are depicted in terms of the chemical shift anisotropy (CSA), leading to a strong variation of the three principal tensor components (δ11, δ22, δ33), unraveling the origin of the experimental 29Si-NMR chemical shift (δiso) differences along the given series. Thus, the Si20 cage is a useful template to further evaluate different environments for encapsulating atomic species.

Local and global aromaticity under rotation: analysis of two- and three-dimensional representative carbon nanostructures.

Nanoscaled 2D and 3D carbon structures with closed curved π-surfaces are of relevance in the development of desirable building units for materials science. Such species are able to sustain local and global aromatic circuits involving isolated regions or the overall structural backbone, respectively. Here we account for local and global aromaticity under rotation of representative two- and three-dimensional species involving para-connected and fused edge-sharing phenyl rings ([8]CPP, [10]CPP, CNB), and C60 fullerene at different charge states. Our results denote that nanoscaled 2D global aromatics mimic the behaviour of the most prototypical aromatic 6π-circuit, given by benzene, where the shielding cone properties vary along the rotation motion. In contrast, 3D spherical aromatics remain almost invariant under rotation, given the distinctive characteristics of such species, differing from 2D global aromatics. Dissection of orbital contributions reveals that π-orbitals are determinants for shifting from non-aromatic to spherical aromatic species. Under rotation, the variation of the anisotropic effect inherent to such nanoscaled structures is accounted for, which is relevant to rationalize variation in NMR signal shifts upon the formation of host-guest aggregates.

Intermediate Silver Doping of Au25(SR)18: Variation of Electronic, Optical, and Chiroptical Properties along Au25-xAgx(SH)18- (x = 0-12) Stoichiometry from DFT Calculations.

The silver analogue of the prominent Au25(SR)18 nanocluster reveals the possibility of finding "gold"-like behavior despite their different nature, in addition to the common features among molecular AgNP. Herein, we explore the effect of successive additions of silver atoms reaching an intermediate Ag/Au doping ratio where the parent gold cluster exhibits properties from both elements. Our results show a more favorable situation as the Ag/Au ratio increases along the Au25-xAgx(SH)18- (x = 0-12) clusters, with structural distortions mainly centered at the ligand-protected shell. The calculated optical spectrum shows that from the Au19Ag6 species, a plasmon-like peak appears along species with a doping ratio above 25%, where all the silver atoms are located within the M12 icosahedron. In addition, the chiral properties were explored, showing mild optical activity from the calculated circular dichroism spectra due to the distorted ligand-shell avoiding a centrosymmetric structure. Thus, an intermediate doping ratio ascribed to a specific structural layer can recover inherent properties to both elements in the binary Au25-xAgx(SH)18- series, suggesting the possibility of having clusters with dual properties at a certain degree of element exchange. This can be useful for further exploration theoretically and synthetically toward different and larger-nuclearity clusters.

Infinitene as two fused helicoidal trails of fused rings: evaluation of the magnetic behavior of [12]infinitene and anionic species displaying global aromaticity and antiaromaticity.

The unique formation of an infinity-shaped carbon backbone made exclusively from fused benzene rings has recently been achieved. The structure of [12]infinitene can be viewed as two fused [6]helicene structures with a central crossover section, depicting a global aromatic behavior along with the overall structure, with deshielding regions along both helicoidal axes. In addition, the 13C-NMR characteristics are discussed. The formation of a cumulative region involving the shielding regions from the aromatic rings is depicted along with the overall aesthetically pleasant structural backbone, which is enhanced at the crossover section. For the evaluated dianionic counterpart, the structure shows a deshielding region above the fused-ring trail and a helicoidal shielding region, ascribed to a global antiaromatic counterpart. The aromaticity is recovered and enhanced at the tetranionic state. Thus, the neutral and tetranionic states are able to build up a long-ranged shielding region, given by the global aromatic behavior, with an enhanced shielding region at the center of the crossover section displaying π-π stacked rings.