Neutral Clusters Research Articles

Growth mechanism of aromatic prebiotic molecules: insights from different processes of ion-molecule reactions in benzonitrile-ammonia and benzonitrile-methylamine clusters.

Benzonitrile (BN, C6H5CN) has been detected in the cold molecular cloud Taurus molecular cloud-1 (TMC-1) in 2018, which is suggested to be a precursor in the formation of more complex nitrogen-containing aromatic interstellar compounds. In this study, we utilized mass-selected infrared (IR) photodissociation spectroscopy and quantum chemical calculations to investigate the structures and gaseous ion-molecule reactions of benzonitrile-ammonia (BN-NH3) and benzonitrile-methylamine (BN-MA) clusters. The spectral observations indicate that the cyclic hydrogen bonding structure predominates in both neutral clusters. After VUV (118 nm) single-photon ionization, a new C-N covalent bond formed between BN and NH3 in the (BN-NH3)+ cluster. However, proton sharing constitutes the primary structure of the (BN-MA)+ cluster. The two nitrogen-containing interstellar molecules react with BN to yield distinct products due to difference in charge distribution and molecular polarity in the ionized clusters. The reactions of BN with other molecules contribute to our understanding of the growth mechanisms of complex interstellar molecules.

Ca n neutral clusters: a two-step G 0 W 0 and DFT benchmark.

Electronic and structural properties of calcium clusters with a varying size range of 2-20 atoms are studied using a two-step scheme within the GW and density functional theory (DFT) with generalized gradient approximation (GGA). The GGA overestimates the binding energies, optimized geometries, electron affinities, and ionization potentials reported in the benchmark. The ground-state structure geometry and binding energy were obtained from the DFT for the ground-state structure of each cluster. The binding energy of the neutral clusters of the calcium series follows an increasing trend, except for a few stable even and odd clusters. The electronic properties of the calcium cluster were studied with an all-electron FHI-aims code. In the G 0 W 0 calculation, the magic cluster Ca10 has relatively high ionization potential and low electron affinity. The obtained ionization potentials from the G 0 W 0 @PBE calculation showed that the larger cluster has less variation, whereas the electron affinities of the series have an increasing trend. The ionization potentials from the G 0 W 0 benchmark for the calcium cluster series have not yet been described in the literature.

Revisiting the quasi-aromaticity in polynuclear metal chalcogenide clusters and their derivative "cluster-assembly" crystalline structures.

The concept of aromaticity is primarily invented to account for the high stability of conjugated organic compounds that possess a specific structural and chemical stability with (4n + 2) π electrons. In 1988, quasi-aromaticity was theoretically proposed for the Mo3S44+ core in the Mo3(μ3-S)(μ-S)3(χ-dtp)3(μ-dtp) L compound (χ: chelating ligand; dtp: (EtO)2PS2-) illustrated by canonical molecular orbitals. However, the origin of the quasi-aromaticity and chemical bonding remains ambiguous, lacking a thorough analysis in terms of stability and quantitative measurement of the aromatic character. Thus, in this work, we systematically reported the electronic structure and aromaticity of a series of polynuclear metal chalcogenide clusters [M3X4(H2O)9]4+ (M = Cr, Mo, W, and Sg; X = O, S, Se, and Te) to explore an efficient tool of NICS index values at specific points to measure the quasi-aromaticity and to figure out the (d-p-d) π three-center bonding as the predominant origin from the arrangement of three Mo atoms and three bridged X atoms. Interestingly, derived from the Mo3⋯S3 quasi-plane, the extended sandwich cluster model of a S3⋯Mo3⋯S3 (Mo3S6) structure can be seen as the seed unit of the popular MoS2 nanomaterials, with the resemblance between both molecular and periodic systems regarding geometries, electronic structures, and chemical bonding. Additionally, the highly symmetric Mo3S4 core in [Mo3X4(H2O)9]4+ can be arranged in a staggered and stacked manner to create the Mo6S82- building block, corresponding to the crystalline structures in BaMo6S8 Chevrel phases, albeit with slight deformations. But the neutral Mo6S8 cluster can be seen as the seed structure for the Mo3S4 periodic materials for the high resemblance in terms of geometry, electronic structures and chemical bonding. Drawing upon the observed similarities between cluster models and materials, we propose a new concept termed "cluster-assembly" materials. This concept involves the expansion from a high-symmetry and/or aromatic stable cluster seed unit to form the corresponding derivative materials, presenting an alternative paradigm for investigating crystals and enriching our comprehension of the stabilities exhibited by both gas-phase clusters and solid-state materials. The concept of "cluster-assembly" materials not only contributes to the formulation of design strategies for novel materials or stable clusters but also provides valuable insights into the extension of periodic aromaticity.

Structure of small yttrium monoxide clusters, chemical bonding, and photoionization: threshold photoionization and density functional theory investigations.

The photoionization (PI) spectra of small gas-phase yttrium monoxide clusters, YnO (n = 1-8), are investigated, and the adiabatic ionization energies are determined. The stable structures are obtained from density functional theory (DFT) calculations. The ground state structures are further confirmed by the CCSD(T) method. The PI spectra are calculated for these stable structures and are compared with the experimental PI spectra. The ground-state structures of the neutral and cation clusters are experimentally assigned with confidence on the basis of a favourable agreement between the experimental and calculated PI spectra. New structures are proposed for Y2O, Y6O, and Y8O compared to the previous literature. Y2O is a linear molecule in the ground state that was previously proposed as a C2v bent molecule. The YnO clusters become 3-dimensional from n ≥ 3. The O atom stays outside, bridging a triangular face of yttrium clusters. Chemical bonding between the yttrium and oxygen atoms is mostly ionic. The excess charge on the oxygen atom is around 1.4e-, transferred from the yttrium atoms bonded with it. Yttrium atoms are mostly covalently bonded. However, for the bigger clusters, free charges of both polarities appear on yttrium atoms that are not bonded with oxygen, indicating ionic interactions. Frontier orbitals consist of mainly delocalized 4d electrons with some 5s contributions, forming Y-Y bonding interactions, but with little contribution and zero contribution from the oxygen orbitals, regardless of the cluster size. The lost electron of YnO+ mostly comes from the 5s orbitals of all Y atoms in the cluster up to size n = 4, and then from 4d-5s hybrid orbitals from n ≥ 5, with the d contribution increasing with size. This is contrary to the previous view in the literature that photoionization occurs from a localized 4d orbital.

Size onset of metallic behavior in neutral aluminum clusters.

The excited state lifetimes of neutral (Al)n clusters up to ∼1 nm in diameter in size, where n ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry. The onset of metallic behavior is identified as a distinct change in the relaxation behavior initiated with single ultraviolet (400 nm) photon excitation. The experimentally measured excited state lifetimes gradually decrease with size for small molecular scale clusters (n < 10) before becoming indistinguishable for larger clusters (n > 9), where the measurements are comparable to electron-lattice relaxation time of bulk Al (∼300 fs). Particularly intense, or magic, Aln clusters do not exhibit any significant excited state lifetime behavior. Time-dependent density functional theory quantify the excited state properties and are presented to show that dynamics are strongly tied to the excited state charge carrier distributions and overlap, rather than detailed changes related to changes in the cluster's electronic and geometric structure. The consistency in excited state lifetimes for clusters larger than n = 9 is attributed to the hybridization of the s- and p-orbitals as well as increasing delocalization. Al3 exhibits unique temporal delay in its transient behavior that is attributed to a transition from triangular ground state to linear structure upon excitation.

Reactions of N2O and CO on neutral Rh10On clusters: a density functional study.

Density functional theory calculations were performed to identify product, reactant and intermediate dissociative/associative structures for the oxygen abstraction and addition reactions: Rh10On + CO → Rh10On-1 + CO2, n = 1-5 and Rh10On + N2O → Rh10On+1 + N2, n = 0-4 reactions. In the case of the oxygen abstraction reactions, the energetics of the reaction path were very similar in energy regardless of the number of oxygen atoms on the Rh10On cluster, whereas for the addition of oxygen to the Rh10On cluster, the reaction was found to become significantly less exothermic with each successive addition of oxygen.

On the energetic and magnetic stability of potassium atomic clusters doped by yttrium.

The abstract should be a single paragraph which summarises the content of the article. This study utilizes density functional theory (DFT) calculations to explore the energetic and magnetic stability of neutral and charged potassium (K) clusters doped with yttrium (Y). We aim to elucidate the influence of Y doping on the energetics and structures of these clusters, comparing them to undoped K clusters. Ground states of 64 polyhedral structures, all of them encapsulating at least one Y atom, were obtained. Y doping generally increased the spin magnetic moment, with charged clusters exhibiting the highest values. Notably, the K12Y+ cluster, possessing an icosahedral geometry and a magnetic moment of 6μB, is classified as a magnetic superatom. Additionally, we identified 14 superatoms with high magnetic robustness. The density of states (DOS) and spin density calculations additionally highlighted the substantial role played by yttrium in the electronic density of the electrons responsible for inducing magnetism in these clusters.

Multi-phosphine-chelated iron-carbide clusters via redox-promoted ligand exchange on an inert hexa-iron-carbide carbonyl cluster, [Fe6(μ6-C)(μ2-CO)4(CO)12]2.

We report the reactivity, structures and spectroscopic characterization of reactions of phosphine-based ligands (mono-, di- and tri-dentate) with iron-carbide carbonyl clusters. Historically, the archetype of this cluster class, namely [Fe6(μ6-C)(μ2-CO)4(CO)12]2-, can be prepared on a gram-scale but is resistant to simple ligand substitution reactions. This limitation has precluded the relevance of iron-carbide clusters relating to organometallics, catalysis and the nitrogenase active site cluster. Herein, we aimed to derive a simple and reliable method to accomplish CO → L (where L = phosphine or other general ligands) substitution reactions without harsh reagents or multi-step synthetic strategies. Ultimately, our goal was ligand-based chelation of an Fe n (μ n -C) core to achieve more synthetic control over multi-iron-carbide motifs relevant to the nitrogenase active site. We report that the key intermediate is the PSEPT-non-conforming cluster [Fe6(μ6-C)(CO)16] (2: 84 electrons), which can be generated in situ by the outer-sphere oxidation of [Fe6(μ6-C)(CO)16]2- (1: closo, 86 electrons) with 2 equiv. of [Fc]PF6. The reaction of 2 with excess PPh3 generates a singly substituted neutral cluster [Fe5(μ5-C)(CO)14PPh3] (4), similar to the reported reactivity of the substitutionally active cluster [Fe5(μ5-C)(CO)15] with monodentate phosphines (Cooke & Mays, 1990). In contrast, the reaction of 2 with flexible, bidentate phosphines (DPPE and DPPP) generates a wide range of unisolable products. However, the rigid bidentate phosphine bis(diphenylphosphino)benzene (bdpb) disproportionates the cluster into non-ligated Fe3-carbide anions paired with a bdpb-supported Fe(ii) cation, which co-crystallize in [Fe3(μ3-CH)(μ3-CO)(CO)9]2[Fe(MeCN)2(bdpb)2] (6). A successful reaction of 2 with the tripodal ligand Triphos generates the first multi-iron-chelated, authentic carbide cluster of the formula [Fe4(μ4-C)(κ3-Triphos)(CO)10] (9). DFT analysis of the key (oxidized) intermediate 2 suggests that its (μ6-C)Fe6 framework remains fully intact but is distorted into an axially compressed, 'ruffled' octahedron distinct from the parent closo cluster 1. Oxidation of the cluster in non-coordinating solvent allows for the isolation and crystallization of the CO-saturated, intact closo-analogue [Fe6(μ6-C)(CO)17] (3), indicating that the intact (μ6-C)Fe6 motif is retained during initial oxidation with [Fc]PF6. Overall, we demonstrate that redox modulation beneficially 'bends' Wade-Mingo's rules via the generation of electron-starved (non-PSEPT) intermediates, which are the key intermediates in promoting facile CO → L substitution reactions in iron-carbide-carbonyl clusters.

Structural and bonding analysis of PtO2− anion and neutral clusters

This study investigates the structures and bonding properties of gas-phase PtO2ˉ anion and PtO2 neutral using anion photoelectron spectroscopy and theoretical calculations. Notably, both species adopt a D∞h symmetric linear O−Pt−O structure, with PtO2 neutral featuring notably shorter Pt–O bond lengths. Charge transfer from the central Pt atom to the terminal O2 motifs is evident in both clusters, as indicated by Natural Population Analysis (NPA). Chemical bonding analysis reveals σ and π double bonding patterns in PtO2ˉ anion, while PtO2 neutral demonstrates σ and π antiaromaticity. This research enhances our understanding of platinum oxide clusters and their potential in developing co-catalysts for efficient solar-driven water splitting.

Spin-orbit coupling of electrons on separate lanthanide atoms of Pr2O2 and its singly charged cation.

Although it plays a critical role in the photophysics and catalysis of lanthanides, spin-orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin-orbit multiconfiguration second-order quasi-degenerate perturbation theory. The energies of six ionization transitions are precisely measured; the adiabatic ionization energy of the neutral cluster is 38 045 (5) cm-1. Most of the electronic states involved in these transitions are identified as spin-orbit coupled states consisting of two or more electron spins. The electron configurations of these states are 4f46s2 for the neutral cluster and 4f46s for the singly charged cation, both in planar rhombus-type structures. The spin-orbit splitting due to the coupling of the electrons on the separate Pratoms is on the order of hundreds of wavenumbers.

CO2 and H2 Activation on Zinc-Doped Copper Clusters.

Here we systematically investigate the CO2 and H2 activation and dissociation on small Cun Zn0/+ (n=3-6) clusters using Density Functional Theory. We show that Cu6 Zn is a superatom, displaying an increased HOMO-LUMO gap and is inert towards CO2 or H2 activation or dissociation. While other neutral clusters weakly activate CO2 , the cationic clusters preferentially bind the CO2 in monodentate nonactivated way. Notably, Cu4 Zn allows for the dissociation of activated CO2 , whereas larger clusters destabilize all activated CO2 binding modes. Conversely, H2 dissociation is favored on all clusters examined, except for Cu6 Zn. Cu3 Zn+ and Cu4 Zn, favor the formation of formate through the H2 dissociation pathway rather than CO2 dissociation. These findings suggest the potential of these clusters as synthetic targets and underscore their significance in the realm of CO2 hydrogenation.

Structural and optical properties of the Agn-tyrosine complexes (n = 3-12): a density functional theory study.

We study the optical properties of Agn (n = 3-12) neutral clusters and their coordination with a tyrosine (Tyr) molecule. A global search strategy coupled with density functional theory (DFT) computations explored the potential energy surface. Adsorption energy calculations predicted that Tyr coordination stabilizes the metal clusters, favouring the Agn-Tyr complexes with an even number of silver atoms. For the Agn low-lying isomers, the general shape and the major transitions of the calculated time dependent-DFT (TD-DFT) absorption spectra align with those of previous reports measured in an argon environment. We use the analysis of non-covalent interactions to identify the specific interactions between each silver cluster and functional groups of Tyr. The TD-DFT absorption spectra for the Agn-Tyr complexes showed that Tyr significantly modifies the optical properties of the coordinated silver clusters and affects the smaller systems to a greater extent. The optical absorption results of the bare Agn clusters and the Agn-Tyr complexes are compared and discussed in detail.

Linear Gold(I) Halide Complexes with a Diamidocarbene Ligand: Synthesis, Reactivity, and Phosphorescence.

A series of halide and pseudohalide gold complexes (DAC)Au(I)X (DAC = N,N'-diamidocarbene; X = Cl, Br, I, and SCN) were prepared in high yields. All complexes possess linear geometry around the gold atom with no aurophilic interactions between neighboring molecules. Reactivity studies for (DAC)Au(I)Cl revealed that the diamido backbone of the carbene ligand is vulnerable to nucleophilic attack by a strong base, potassium tert-butoxide, resulting in cleavage of the carbene backbone and formation of a neutral trigold cluster. Halide and pseudohalide complexes are bright phosphorescent emitters in the solid state, exhibiting photoluminescence quantum yields up to unity. Phosphorescence occurs in the range 480-520 nm with lifetimes as short as 1 μs, resulting in fast radiative rates up to 9.4 × 105 s-1 which is on par with the most efficient heavy metal emitters. Photophysical properties are explained by the intrinsic π-accepting nature of the DAC carbene and are supported by TDDFT calculations.

A Computational Exploration of Exohedrally Transition Metal Doped Si94- Superatom Based Magnetic MSi9M' Clusters (M, M' = Sc(II) to Cu(II)).

Nanosized clusters are drawing immense attention of the scientific community due to their size and composition dependent tunability of physical and chemical properties. Silicon nanoclusters are especially important because of their abundance and ample utility in the domains of electronics and semiconductor industry. Zintl phases of Si offer an excellent opportunity in the domain of nanocluster research owing to their superior stability and multifarious possibilities of tunability of electronic properties through doping with other elements. Doping silicon clusters with transition elements is a prevalent strategy to induce magnetic properties in such clusters. Although doping silicon clusters with single transition metal atoms can induce significant magnetism in nanoclusters, the dominant covalent interaction between silicon and the transition metal causes the magnetic moment to quench. The rational strategy of inducing a sustainable magnetic moment can be to introduce ferromagnetic interaction between two sites carrying nonvanishing magnetic moments. In the present work, such a possibility is explored in terms of the stability of the clusters and corresponding magnetic exchange coupling in them. The Si94-superatomic cluster is doped with two transition metal atoms exohedrally and the neutral clusters designed thereby are investigated computationally if they reduce or reinforce the high stability of the superatom and substantiate the possibility of obtaining nanosized magnetic units as building blocks of tunable materials for various applications.

High nuclearity heterometallic [Fe7Ln4] neutral coordination clusters with electrocatalytic activity for water oxidation

Three mixed metal iron-lanthanide isostructural clusters formulated, [Fe7Ln4(μ4-O)3(μ3-O)(μ3-OH)2(μ2-OH)(mdea)6(κ1-OAc)(κ2-OAc)3(μ-OAc)6(H2O)].nH2O where {n = 1.0, 2.5 and 0.5 for Ln = Nd (1), Pr (2), and Eu (3), respectively} are prepared by the reaction of FeCl2·4H2O and Ln(NO3)3·6H2O with N-methyldiethanolamine (mdea) and CH3COO−. The core of these compounds is irregular tent-like clusters. In these structures, the central Fe is bridged to another Fe in the cluster ball by (μ4-O)3(μ3-O) and with bridged Ln2 with two (μ3-OH) ions. All these clusters were investigated as electrocatalysts for water oxidation. The results illustrate that 1 is the most efficient material for water oxidation with overpotential of 309 mV and Tafel slope of 100 mV dec−1 in neutral media. This is due to the larger electrochemical active surface area and more active catalytic sites of this cluster compared to Fe7Pr4 and Fe7Eu4 clusters. The electrocatalytic behavior of these clusters during bulk electrolysis is similar. In all 1–3, a yellow thin film is formed on the surface of electrode during water oxidation. The analyses show the presence of iron oxide and Ln oxide as the main components in this film. Long-term stability testing confirms that the film is active in the reaction, but its level activity depends on the nature of lanthanides present.

Theoretical study on structural evolution, photoelectron and vibrational spectra, and thermochemistry properties of neutral, anionic and di-anionic titanium-doped tin (TiSnn0/−/2− (n = 4–17)) nanoalloy clusters

The structural evolution, chemical stability, electronic and vibrational properties, as well as charge transfer and bonding character of TiSnn0/−/2− (n = 4–17) clusters have been performed with density functional theory calculations using ABCluster search technique. Structurally, it is found that the growth patterns prefer three kinds of absorbed stages from polygonal bipyramidal configuration for n = 4–6, to absorbing additional Sn on the adjacent surfaces of pentagonal bipyramid unit from n = 7–12, and finally to the TiSn130/−/2− cluster as the first foundational architectures, of which the encapsulated cage structure is formed when n = 11. The simulated PES spectra agree with available experiments. More interestingly, the neutral TiSn16 cluster not only possesses the high thermodynamic and relative stability but also preferable photochemical reactivity, that can be further explained by superatom features and delocalized multi-center bonds (AdNDP), while the strong p-d hybridization between Ti atom and Sn unit plays an important role in the stabilities of clusters, making it as the most suitable building units. In addition, the UV–Vis absorption spectra of TiSn16 are discussed, and the main transitions of crucial excited states are analyzed in detail. The Infrared and Raman vibrational characteristic peaks of all these neutral and charged species are properly assigned, of which the TiSnn0/−/2− (n = 10–17) clusters possess degenerating deformation mode of Ti atom wagging in Sn cage framework (Infrared active) and breathing mode of Sn cage framework (Raman active). All these findings will provide a further understanding for the nanoalloy cluster as the most suitable building block with further development as a potential optoelectronic material.

Cooperativity and Frustration Effects (or Lack Thereof) in Polarizable and Non-polarizable Force Fields.

Understanding cooperativity and frustration is crucial for studying biological processes such as molecular recognition and protein aggregation. Force fields have been extensively utilized to explore cooperativity in the formation of protein secondary structures and self-assembled systems. Multiple studies have demonstrated that polarizable force fields provide more accurate descriptions of this phenomenon compared to fixed-charge pairwise nonpolarizable force fields, thanks to the incorporation of polarization effects. In this study, we assess the performance of the AMOEBA polarizable force field and the AMBER and OPLS nonpolarizable pairwise force fields in capturing positive and negative cooperativity recently explored in neutral and charged molecular clusters using density functional theory. Our findings show that polarizable and nonpolarizable force fields qualitatively reproduce the relative cooperativity observed in electron structure calculations. However, AMBER and OPLS fail to describe absolute cooperativity. In contrast, AMOEBA accounts for the absolute cooperativity by considering interactions beyond pairwise interactions. According to the energy decomposition analysis, it is observed that the electrostatic interactions calculated with the AMBER and OPLS force fields seem to play an important and counterintuitive role in reproducing the adiabatic interaction energies calculated with density functional theory. However, it is important to note that these force fields, due to their nature, do not explicitly incorporate many-body effects, which limits their ability to accurately describe cooperativity. On the other hand, frustration in polarizable and nonpolarizable force fields is caused by changes in bond stretching and angle bending terms of the building blocks when they are forming a complex.

Coupled-Cluster Density-Based Many-Body Expansion.

While CCSD(T) is often considered the "gold standard" of computational chemistry, the scaling of its computational cost as N7 limits its applicability for large and complex molecular systems. In this work, we apply the density-based many-body expansion [ Int. J. Quantum Chem. 2020, 120, e26228] in combination with CCSD(T). The accuracy of this approach is assessed for neutral, protonated, and deprotonated water hexamers, as well as (H2O)16 and (H2O)17 clusters. For the neutral water clusters, we find that already with a density-based two-body expansion, we are able to approximate the supermolecular CCSD(T) energies within chemical accuracy (4 kJ/mol). This surpasses the accuracy that is achieved with a conventional, energy-based three-body expansion. We show that this accuracy can be maintained even when approximating the electron densities using Hartree-Fock instead of using coupled-cluster densities. The density-based many-body expansion thus offers a simple, resource-efficient, and highly parallelizable approach that makes CCSD(T)-quality calculations feasible where they would otherwise be prohibitively expensive.

Comparison of Magnetic Deflection among Neutral Sodium-Doped Clusters: Na(H2O)n, Na(NH3)n, Na(MeOH)n, and Na(DME)n.

Using a pulsed Stern-Gerlach deflection experiment, we present the results of a comparative study on the magnetic properties of neutral sodium-doped solvent clusters Na(Sol)n with n = 1-4 (Sol: H2O, NH3, CH3OH, CH3OCH3). Experimental deflection ratios are compared with values calculated from molecular dynamics simulations. NaNH3 and NaH2O are deflected as a spin 1/2 system, consistent with spin transitions occurring on a time scale significantly longer than 100 μs. For all other clusters, reduced deflection is observed. The observed magnetic deflection behavior is correlated to the number of thermally populated rotational states in the clusters. We discuss that spin-rotational couplings allow for avoided crossings and a reduction in the effective magnetic moment of the cluster. This work attempts to understand the evolution of magnetic properties in isolated weakly bound clusters and is relevant to diamagnetic and paramagnetic species expected to exist in solvated electron systems.

Single-Photon Ionization Induced New Covalent Bond Formation in Acrylonitrile(AN)-Pyrrole(Py) Clusters.

The formation of nitrogen-containing organic compounds is crucial for understanding chemical evolution and the origin of life in the interstellar medium (ISM). In this study, we explore whether acrylonitrile (AN) and pyrrole (Py) can form new nitrogen-containing compounds after single-photon ionization in their gaseous clusters by vacuum ultraviolet (VUV)-infrared (IR) spectroscopy and theoretical calculations. The results show that a strong linear H-bond is formed in neutral AN-Py, while cyclic or bicyclic H-bonded networks are formed in the neutral AN-Py2 cluster. It is found that the structure containing a new C-C covalent bond between two moieties in (AN-Py)+ is formed besides the formation of H-bonded structures after AN-Py is ionized by VUV light. In (AN-Py2)+ cluster cations, new C-C or C-N covalent bonds tend to be formed between two Py, with (Py)2+ as the core in the cluster. The results reveal that new covalent bonds are more likely to be formed between two Py species when AN and Py are present in the cationic clusters. These results provide spectroscopic evidence of the formation of new nitrogen-containing organic compounds from AN and Py induced by VUV, which are helpful for our understanding of the formation of diverse prebiotic molecules in interstellar space.