Alvaro Muñoz-Castro

Alvaro Muñoz-Castro
Universidad Autónoma De Chile · Dirección de Postgrado e Investigación

PhD

About

247
Publications
19,083
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
2,529
Citations
Additional affiliations
April 2014 - present
Universidad Autónoma De Chile
Position
  • Research Associate
March 2011 - March 2014
Universidad Andrés Bello
Position
  • Professor (Assistant)

Publications

Publications (247)
Article
The isostructural and isoelectronic silver [Ag25(SR)18]- (R=Ligand) cluster to [Au25(SR)18]- gold clusters allows to further understand the fundamental similarities between Au and Ag, at the ultrasmall nanoscale (< 2 nm)...
Article
The controlled structural modification of ligand-protected gold clusters is evaluated by a proper variation of the size and shape of N-heterocyclic carbene (NHC) ligands. Density functional theory calculations show that the Au13 core of [Au13(NHC)8Br4]+ can be shaped into an icosahedron and/or a so far unexpected cuboctahedron depending on the ster...
Article
Efficient and affordable synthetic nanometric hosts able to incorporate different species have attracted attention for further exploration of changes in chemical properties and reactivity at the nanomolecular scale. The recent incorporation of suit[3]ane, involving a host composed by two parallel hexameric platforms alternating pyridinium and pheny...
Article
Full-text available
Understanding the structural changes taking place during the assembly of single atoms leading to the formation of atomic clusters and bulk materials remains challenging. The isolation and theoretical characterization of medium-sized clusters can shed light on the processes that occur during the transition to a solid-state structure. In this work, w...
Article
Full-text available
Orbital contributions to the magnetic response depend on the method used to compute them. Here, we show that dissecting nuclear magnetic shielding tensors using natural localized molecular orbitals (NLMOs) leads to anomalous core contributions. The arbitrariness of the assignment might significantly affect the interpretation of the magnetic respons...
Article
In this work, we synthesize naked tin cluster anion Sn 36 8‒ , representing the first example of pure Sn nanowire assembled through oxidative coupling reactions of a super atomic cluster Sn 9 ⁴⁻ . Theoretical...
Article
In this work, we have performed a computational study on the structure and electronic properties for Be-doped Ptn (n = 1-12) clusters in the framework of density functional theory (DFT). The most stable structures of the clusters are obtained by a structure search procedure based in simulated annealing. The results show that the PtnBe clusters adop...
Article
In this work, we report the synthesis and characterization of two novel Ru-containing Zintl clusters: [Sn19{Ru(COD)(en)}2]4− and [Sn20{Ru(COD)}2]6−. The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms. The single-cry...
Article
Atomically precise gold superatoms are useful building blocks whose properties can be tuned by the proper choice of ligands in the protecting ligand layer. Herein, different N-heterocyclic carbene (NHC) derivatives of the prototypical [Au11(PPh3)8Cl2]+ cluster were evaluated by the replacement of a single ligand, which led to isoelectronic [Au11(PP...
Article
A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent...
Article
Full-text available
Copper plays an important role in alkyne coordination chemistry and transformations. This report describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support. Details of the related copper(I) complex of HCºCSiMe3 are also reported. They are three-...
Article
Full-text available
A chemical bonding of several metallabenzenes and metallabenzynes was studied via an adaptive natural density partitioning (AdNDP) algorithm and the induced magnetic field analysis. A unique chemical bonding pattern was discovered where the M=C (M: Os, Re) double bond coexists with the delocalized 6c-2e π-bonding elements responsible for aromatic p...
Article
Full-text available
The experimentally characterized hexamethylbenzene dication C6(CH3)62+ shows a pentagonal-pyramidal structure involving a carbon-capped five-membered ring. The structural characterization of this hypercoordination (or hypervalency) gives rise if the aromatic behavior remains in the resulting pentagon ring. Here, we investigated the induced magnetic...
Article
The rational synthesis of well-defined clusters requires further understanding of the fundamental aspects related to the stabilization of preferred isomers over other possible species. Atomically-precise gold superatoms offer useful templates to evaluate the role of the characteristics of the ligand shell in the resulting structure. Herein, we expl...
Article
Unraveling the different contributing terms to an efficient anion encapsulation is a relevant issue for further understanding of the underlying factors governing the formation of endohedral species. Herein, we explore the favorable encapsulation of hydride and halide anions in the [Ag8(X){S2P(OPr)2}6]+ (X- = H, 1, F, 2, Cl, 3, Br, 4, and, I, 5) ser...
Article
The structural evolution of Tin (n=33−60) clusters has been investigated by using the systematic cluster growth method together with the many‐body Gupta potential. The lowest energy structures are further refined by using density functional theory computations within the accuracy of the Perdew‐Burke‐Ernzerhof (PBE) exchange‐correlation functional a...
Article
Full-text available
Polyfluorinated, electron-withdrawing, and sterically demanding supporting ligands are of significant value in chemistry. Here we report the assembly and use of a bis(pyrazolyl)borate, [Ph2B(3-(SF5)Pz)2]- that combines all such features, and involves underutilized pentafluorosulfanyl substituents. The ethylene and carbonyl chemistry of copper(i) su...
Article
Spatial race under low oxygen conditions requires solid mild propellants to be used. Therefore, we study the catalytic effect of the previously reported [trans-Cu(μ-OH)(μ-dmpz)]6 complex on the thermal decomposition of ammonium perchlorate by a differential scanning calorimetry (DSC) technique. The copper compound causes a decrease of ammonium perc...
Chapter
The ability to incorporate guest species in appropriate molecular host offers a unique opportunity to explore and learn about confinement effects provided by sterically and electronically restrained environments. Cyclophane structures are prototypical examples of well-defined host species providing efficient environments for guest inclusion, allowi...
Article
Ligand-protected gold clusters are usually understood in terms of the superatom concept, where certain species are able to behaves as prototypical molecules. Here, we discuss the metalloid cluster Au70S20(PPh3)12 in terms of the bonding characteristics of its inner 18-cluster electron Au224+ core. Our interpretation is based on a SP3-hybridized cor...
Article
Full-text available
Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M2(CO)6Sn2Sb5]³⁻ (M = Cr, Mo), and [(MSn2Sb5)2]⁴⁻, (M = Cu, Ag)) in...
Article
Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold-phosphine M13(dppe)6 cluster, as a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1-3 nm size range, via relat...
Article
Synthetic exploration and theoretical characterization of metal clusters are actively developing branches of modern inorganic chemistry. Advances in these areas constantly expand the rich structural diversity of viable species, allowing a detailed study of the fundamental characteristics of bench‐stable compounds. In this minireview, we summarize r...
Article
Host-guest chemistry is a relevant issue in materials science, which encourages further development of versatile host structures. Here the particular features of coinage-metal pillarplexes are evaluated towards formation of host-guest aggregates by the inclusion of 1,8-diaminooctane, as characterized for [M8(LMe)2]4+ (M = Ag, and, Au). The obtained...
Article
Recently, P. V. Nhat et al., have discussed and commented on our article (DOI: 10.1039/D0CP04018E) for the case of the most stable structure of Ag15. They have found a new most stable structure (labeled as 15-1) in comparison to the putative global minimum reported by us, which is a four layered 1-4-6-4 stacking structure with a C2v point group (15...
Article
The hydrogen storage properties of Ti-doped Bn ( n = 3 − 12 ) clusters are investigated by using the “diatomic deposition method” with further evaluation by density functional theory computations. The results show that TiBn ( n = 7 − 9 ) clusters possess the ability to storage up to four H2 molecules, reaching a mass fraction of 6.12%. Further, the...
Preprint
Full-text available
In this work, we synthesized and isolated a continuous 24-atom cluster Ge 24 ⁴⁻ , which was characterized by X-ray diffraction analysis and Energy-dispersive X-ray spectroscopy, showing an elongated worm-like structural characteristic. Theoretical analysis reveals that electron delocalization plays a vital role in the formation and stabilization of...
Article
The structure, electronic and reactivity properties of PtnCun (n = 1-7) clusters are investigated in the framework of density functional theory (DFT). The most stable forms of the clusters are obtained by a structure search procedure based in simulated annealing. The results show that the PtnCun cluster alloys adopt layered structure motifs with se...
Article
The first Zintl cluster containing distorted Bi6 triangular prism, [Bi6Mo3(CO)9]4−, has been synthesized and structurally characterized. Quantum chemical calculations indicated that the distorted cage cluster features multiple local σ-aromaticity.
Article
An inverse sandwich‐type cluster dimer of [K(2,2,2‐crypt)]4{[K2ZnSn8(ZnMes)]2} was synthesized. The highly charged [Sn8]⁶⁻ is captured by mixed‐valence ZnI/ZnII to form the closo‐[Zn2Sn8] bridged by a ZnI‐ZnI bond. The Zn–Sn compound not only indicates the [Sn8]⁶⁻ can act as a novel bridging ligand like arene, but shows the interdisciplinary integr...
Article
Since [Sn 8 ] 6‐ was discovered from the solid‐state phase in 2000, its solution chemistry has been elusive due to the high charges and chemical activity. Herein, we report the synthesis and characterization of an inverse sandwich‐type cluster dimer {[K 2 ZnSn 8 (ZnMes)] 2 } 4‐ ( 1a ), in which the highly charged [Sn 8 ] 6‐ is captured by mixed‐val...
Article
Main observation and conclusion Two ternary clusters, [As3Nb(As3Pb3)]3‐ 1 and [As3Ta(As3Pb3)]3‐ 2, were directly extracted from “K8NbPbAs5” and “K8TaPbAs5” intermetallic solid respectively in the presence of ethylenediamine and 2.2.2‐crypt. Both 1 and 2, comprising an electron‐poor early transition metal‐atom Nb or Ta coordinated to a As3 triangle...
Article
Dications of cycloparaphenyles ([n]CPPs) are known to exhibit in‐plane global aromaticity, contained in a nanobelt structure. Recently synthesized ortho and meta isomers of [n]CPPs break the radial symmetry of π structure incorporating perpendicular oriented π orbitals. Herein we set to explore the aromaticity of neutral and dicationic ortho and me...
Article
The formation of π-aromatic circuits along a grossly warped nanographene, C 80 H 30 , containing five- and seven-membered rings inserted into a six-membered mesh, reveals global π-circuits at the edge of the backbone....
Article
The systematic cluster growth (SCG) is a biased structure search strategy based in a seeding process for investigating the structural evolution and growth pattern of transition metal clusters. In SCG, a set of initial structures with size n are constructed based on the equilibrium structures of the preceding n-1 cluster isomers by adding a single a...
Article
Full-text available
The Cover Feature shows that 1‐butene molecules can penetrate into a dense crystalline solid and drive the transformation of planar trinuclear fluorinated copper(I) pyrazolate complexes toward boat‐shaped, dinuclear copper‐butene adducts. The chemistry of these complexes with 1‐butene is also examined in solution, and a comparison with analogous ad...
Article
Ethylene complexes of gold(I) have been stabilized by electron-rich, κ2-bound tris(pyrazolyl)borate ligands. Large up-field shifts of olefinic carbon NMR resonances and relatively long C=C distances of gold bound ethylene are...
Article
The use of different N-heterocyclic carbene (NHC) as dative ligands benefits from their capabilities ranging from strong to weak σ-donor according to the Tolman electronic parameter (TEP), well spread in the formation of monometallic complexes, and recently extended to metallic nanocluster and surfaces. Here, we set to explore the role of relativis...
Article
Full-text available
Following an ongoing interest in the study of transition metal complexes with exotic bonding networks, we report herein the synthesis of a family of heterobimetallic triangular clusters involving Ru and Pd atoms. These are the first examples of trinuclear complexes combining these nuclei. Structural and bonding analyses revealed both analogies and...
Chapter
After more than 150 years since the Kekule's conceptualization of the benzene structure, this small hexagonal hydrocarbon indubitably remains the most prototypical example of aromaticity. Recent developments revealed that aromaticity is not limited by canonical carbon, hydrogen, or nearby elements but also covers almost all periodic table. Moreover...
Article
We report the synthesis, characterization and computational analysis of coinage metal-ether complexes supported by N-heterocyclic carbenes (NHC), SIPr and Et2CAAC. The related water adducts are also included. The [(NHC)M]+(M = Cu, Ag, Au) species show the notheworthy ability to bind Et2O and H2O. This interaction towards Et2O and H2O is partly ascr...
Article
Anions show relevant roles in biological routes. The supramolecular chemistry investigates the chemical bonding between two or more molecules and/or ions. Here, the nature of the bond between the chloride anions and macrocycle receptors elaborated from: i) pyridine; ii) pyrrole; iii) borazines; iv) triazine; and v) 1,2,3–triazole, rings are studied...
Article
This perspective focuses on the crucial role that energy decomposition schemes play in elucidating the physical nature of non-covalent interactions in supramolecular systems, particularly from the point of view of host-guest systems stabilized by non-covalent interactions, which are fundamental to molecular recognition. The findings reported here r...
Article
In the present work, the lowest energy structures and electronic properties of Ag n clusters up to n = 16 are investigated using a successive growth algorithm coupled with density functional theory calculations (DFT). In the literature, a number of putative global minimum structures for silver clusters have been reported by using different approach...
Article
We report the molecular and electronic structure, and the calculated electronic excitation energies, using the time dependent density functional methodologies (TD-DFT), and the induced magnetic field (Bi) of a series of Cu(I) dithiolato and diselenolato species of formula [Cu8(L)6]. They are composed by eight copper atoms forming a Cu8 cube and six...
Article
The synthesis and characterization of hetero–multimetallic complexes have been one of the biggest challenges to inorganic chemists in the last years. Here, the physical nature behind the relative stability of tri–heteronuclear complexes, involving the [M(PR3)]+ (M = Au(I), Ag(I) and Cu(I); and R = Ph and H) cation bridged by the [Fe(CO)4]2– anion,...
Article
The recent development of compounds for recognizing ions highlights the applicability of this area. In this work, the simultaneous recognition of cations (Li⁺, Na⁺ and K⁺) and anions (F⁻, Cl⁻ and I⁻) using a macrocycle comprising a simple crown ether and an iodine-triazole unit is investigated. The roles of the (i) cation radius, (ii) anion radius,...
Article
Thorium encapsulated metallofullerenes (Th-EMFs) with external C76, C80, C82, and C86 cages have been synthesized, with the 13C-NMR spectrum recorded for Th@C82. Here, we explore computationally the chemical bonding, NMR and spherical aromaticity of Th@C82 and related thorium-encapsulated metallofullerenes. Our results show that these Th-EMFs are n...
Article
Full-text available
Sandwich-type clusters with the planar fragment containing a heterometallic sheet have remained elusive. In this work, we introduce the [K(2,2,2-crypt)]4{(Ge9)2[η⁶-Ge(PdPPh3)3]} complex that contains a heterometallic sandwich fragment. The title compound is structurally characterized by means of single-crystal X-ray diffraction, which reveals the p...
Article
The formation of supramolecular aggregates incorporating C60 fullerenes can be followed and characterized by nuclear magnetic resonance (NMR) measurements. Here, we unravel the particular patterns provided by zinc‐porphyrin (ZnP)‐bridged dimers, where the aromatic character of each ZnP unit leads to an enhanced shielding region for the closest full...
Article
Full-text available
The structure and bonding of a series of selected phosphine-protected gold clusters (Aun-P) of nuclearity varying from n = 6 to 13 were investigated by density functional theory (DFT) calculations and compared to those of the hypothetical homologues in which phosphines were replaced by N-heterocyclic carbene (NHC) analogues (Aun-C). Both the Aun-P...
Article
The isolated‐pentagon rule (IPR) is a determining structural feature accounting for hollow fullerene stabilization and properties related to Cn (n ≥ 60) cages. The recent characterization of an unprecedented non‐IPR hydrofullerene, C2v‐C66H4, bearing two heptagons with adjacent fused‐pentagons motif, largely dismiss this feature. Herein, employing...
Article
DFT calculations were carried out on bare Au32 and Au33 nanoclusters with various charges, in order to analyze their stability with respect to different cluster electron numbers. Results indicate that in addition to the neutral Au32 hollow species, significant HOMO-LUMO gaps are computed for [Au32]8+ (hollow) and [Au32]4+ (two-shell structure). Spe...
Article
The doped deltahedral Zintl clusters are known for decades. Here, we report a functionalized doped organo-Zintl clusters [Ge7P2R3](R = CH3, C2H5 & C3H3) derived from the doped [Ge7P2]²⁻ Zintl ion by replacing germanium atoms in deltahedral Ge9⁴⁻ cluster with Phosphorus (P). Using first principle calculation, we show that, it is also possible to des...
Article
The NMR characterization of small C36 hollow fullerene exposes a stable cage with structural features based on its strained curved π‐surface in a D6h‐symmetry. Our results indicate that planar‐like aromatic properties of the D6h‐C36 isomer decrease to a nonaromatic cage for D2d‐C36 after Stone‐Wales transformation of an equatorial [6.6] bond. This...
Article
The vertex-substituted icosahedral cluster ion [Cp*RuPb11]³⁻ (1) forms from the reaction between K4Pb9 and [RuCp*(cod)Cl] (cod = 1,5-cyclooctadiene) in ethylenediamine (en) / toluene solvent mixtures. The endohedral Cu(+1) derivative, [Cu@Cp*RuPb11]²⁻ (2), is prepared similarly but with [Cu(PPh3)3Cl] added into the reaction mixture. The [K(en)2(18-...
Article
A new structure for spherical fullerene is evaluated involving sixty phenylene rings, replacing every C-vertex from C60, which is based on the isolated-pentagon-rule (IPR) motif based on a cyclo‐meta‐phenylene derivatives reported by Isobe group, resulting in superstructures mimicking C60 (1). Density functional theory calculation shows its stabili...
Article
The physical nature of the Host-Guest (HG) interactions occurred between molecular triangles and linear anions were explored using Density Functional Theory (DFT) calculations combined with energy decomposition analyses (EDA), nuclear independent chemical shift (NICS), and non- covalent interactions (NCI). We demonstrated that: (i) in addition to t...
Article
The Cover Feature illustrates a journey from flatland to 3D‐space, showcasing research by Prof. Alvaro Muñoz‐Castro at the Facultad de Ingeniería, Universidad Autónoma de Chile, Chile (photo credit: Steve Baxter). Dual planar‐planar, planar‐spherical, and spherical‐spherical species show two separate aromatic regimes sharing shielding regions of mo...
Article
The geometrical, electronic and catalytic properties of PtnAgn (n = 1–7) clusters are investigated by means of density functional theory (DFT) computations. The ground state structures are obtained by a structure search procedure based in the simulated annealing method. In general, the PtnAgn clusters adopt structures with Pt cluster motifs at the...
Article
Driven by strong 3c–2e Zn–Ge–Ge or Cd–Ge–Ge interactions, two unprecedented supertetrahedral clusters [Zn6Ge16]⁴⁻ and [Cd6Ge16]⁴⁻ were synthesized through the assembly of [Ge4]⁴⁻ and transition metal precursors. This strategy provides not only a new method to obtain large heterometallic clusters, but also a new conceptual understanding of how σ‐aro...
Article
Molecular recognition is the key driver in the formation of supramolecular complexes, enabling the selective encapsulation of specific guests. Here, we explore the delicate balance between different energetic terms in the formation of an efficient host for fluoride anions based on a cylindrophane structure, which can be achieved by the incorporatio...
Article
Endohedral metallofullerenes are key species for expanding the range of viable fullerenes, their versatility, and applications. Here we report our results on the formation of spherical aromatic counterparts of the C60 fullerene, based on the inclusion of Cr, Mo and W endohedral atoms. The resulting M@C60 endohedral fullerenes are 66-π electron neut...
Article
We investigate the structural, electronic, and chemical properties of Cun (n = 1 − 12) clusters doped with a single Ru atom. Geometry after global optimizations for RuCun clusters, at n < 7, is similar to the corresponding for pure Cun+1. From n = 8 to 10, the Ru atom is highly coordinated, coming from dome-shaped structures to their total encapsul...
Article
Here we discussed the plausible formation of the Cu10Ru cluster as a superatomic specie accounted its 1S²1P⁶1D¹⁰ shell order. By stochastic structure search on Cu10Ru clusters, we found six low-lying cluster isomers with ΔE values from 0.0 to 4.7 kcal∙mol above the ground state denoting an endohedral motif with the Ru dopant inside the Cu10 cage. B...
Article
In this work, the largest heterometallic supertetrahedral clusters, [Zn6Ge16]4– and [Cd6Ge16]4–, were directly self‐assembled through highly‐charged [Ge4]4– units and transition metal cations, in which 3‐center‐2‐electron σ bonding in Ge2Zn or Ge2Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures hav...
Article
The shielding cone concept is one of the most characteristic aspects of planar aromatic species. Here, we explored how two neighbor aromatic moieties behave as dual planar‐planar, planar‐spherical, and spherical‐spherical species given by biphenyl, [PhCB 11 H 11 ] ‐ , and [CB 11 H 11 ] 2 2‐ , respectively. Our results show two separate aromatic reg...
Article
In this work, we report a dimeric cluster anion {[CuGe 9 Mes] 2 } ⁴⁻ , which was isolated as the [K(2,2,2-crypt)] ⁺ salt and characterized by single-crystal X-ray diffraction and ESI mass spectrum. The title cluster...
Article
Full-text available
The induced magnetic field of C2N (N = 3-14) carbon rings was dissected to contributions from out-of-plane and in-plane π orbitals revealing two concurrent long-range shielding or deshielding cones as a manifestation of the dual aromatic and antiaromatic character of C4n+2 and of C4n rings respectively. Aromaticity based on the magnetic criterion w...
Article
Dinuclear Cu II complexes with 3,5-dinitrobenzoates and 2,2′-bipyridine (2) or 1,10-phenanthroline (3) were synthesized and characterized. A complete energy framework analysis using the HF/3-21G energy model was performed which found that dispersion forces and C—H...O interactions are responsible for the crystal structure features. The magnetic pro...