Planarity does not always mean higher aromaticity – Intriguing metalloaromaticity of three Al13+ isomers

Guin, Surajit; Ghosh, Sourav Ranjan; Jana, Atish Dipankar

doi:10.1016/j.jmgm.2020.107544

Cited by 6 publications

(5 citation statements)

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“…In fact, aromaticity was even deemed to be modified or controlled to represent a design opportunity . Although it is most popular in the study of traditional organic systems like benzene, coronene, etc., it is commonly used even in metal-bearing systems, where it is often called metallo-aromaticity . Recently, a shell (geometrical) model has been suggested that combines the role of aromaticity with topology and symmetry. − By using a topological and electronic shell structure inherent in hexagonal PAHs, it has been shown how the celebrated Hückel and Clar rules , for aromaticity and stability could be derived and connected to shell closures, with well-identified stability and aromaticity maxima versus number of π-electrons that resemble the ionization energy curves of the elements versus the atomic number.…”

Section: Basic Theorymentioning

confidence: 99%

“…Recently, a shell (geometrical) model has been suggested that combines the role of aromaticity with topology and symmetry. − By using a topological and electronic shell structure inherent in hexagonal PAHs, it has been shown how the celebrated Hückel and Clar rules , for aromaticity and stability could be derived and connected to shell closures, with well-identified stability and aromaticity maxima versus number of π-electrons that resemble the ionization energy curves of the elements versus the atomic number. Despite the above and the fact that compounds said to be aromatic are generally flat, as they tend as such to possess extreme stability, cases exist where planarity does not mean higher aromaticity. For example, the minimum of the Al 13 + structure (no imaginary frequency) has been predicted to be nonplanar, although it is more aromatic and shows a higher electron delocalization than two nearby planar geometries (saddle points).…”

Section: Basic Theorymentioning

confidence: 99%

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Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Varandas

2023

J. Phys. Chem. A

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Using our recently suggested concept of a quasi-molecule (“tile”) and, in the case of the planarity here at stake, its generalization to larger than tetratomics, we explain why carbon [n]triangulenes tend to be planar, while hybrids, where just a few or even all a- or b-type carbon atoms are silicon-substituted (sila-[n]triangulenes), tend to be planar/nonplanar when compared with the unsubstituted carbon-[n]triangulenes. Because other spin states of the parent carbon- and sila-[n]triangulenes tend to correlate with the same tiles, it is conjectured that no structural changes are expected to depend on their spin state. Other polycyclic and sila-compounds are also discussed.

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Section: Basic Theorymentioning

confidence: 99%

Section: Basic Theorymentioning

confidence: 99%

Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Varandas

2023

J. Phys. Chem. A

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“…Here in the current paper, we report the effect of doping of alkali atoms Li, Na and K at the core of the recently reported planar and quasi-planar Al 13 + clusters by our group [16,17]. It was found that Al 13 + cluster can exist in three closely lying isomeric form, a perfectly planar cluster, and two quasi-planar clusters, slightly puckered in opposite direction with respect to the planar cluster.…”

Section: Introductionmentioning

confidence: 83%

Effect of Alkali Atom Doping on the Electronic Structure and Aromatic Character of Planar and Quasi-Planar Al13+ Clusters

Guin¹,

Jana²

2021

Preprint

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A set of three Al13+ clusters, one perfectly planar and two quasi-planar structures have been recently reported by our group [Guin et. al. Journal of Molecular Graphics and Modeling, 2020, 97, 107544]. One of the quasi-planar structures is true minima (GS) with zero imaginary frequency and another one is transition state structure (TS) with one imaginary frequency, whereas the perfectly planar structure has three imaginary frequencies. All three posses bilaterally symmetry with identical structural features - a set of ten aluminium atoms encircle a triangular core and also this set of three aluminium cluster is a rare example of a metallo-aromatic system in which highly anti-aromatic islands are embedded in an aromatic sea. One of the atoms of the central triangle lies on the symmetry axis and is crucial for the stability of these clusters. In the present study, we have explored the effect of doping alkali atoms (Li, Na and K) at this pivotal site of the cluster with an aim to understand the structural stability and the effect on the aromatic character as compared to the parent clusters. Besides the electronic structural analysis, NICS and ELF studies have also been carried out to characterize the aromatic nature of the doped clusters. Interestingly it has been found that even with the incorporation of the alkali atoms the bilateral symmetry of the clusters remains intact but instead of the central position the alkali atoms drift towards the periphery of the cluster along the symmetry line and equilibrate on the periphery. The dipole moment of the clusters systematically increases and the overall aromaticity of the cluster systematically decreases with the increase in the atomic number of the dopant alkali atoms.

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“…Besides we have extended the study to our recently reported a rare set of three isomers of Al 13 + cluster one of which is perfectly planar (CI) and two others are quasi-planar (CT and CII) in natures. Among the two quasi-planar clusters CII is the global minimum energy with its exible tail region disposed upwards whereas that of the other quasiplanar cluster CT is con gured downward of the mean plane of the clusters [19,20]. Like poyacene molecules [21] which show interesting plasmonic property due to their characteristic aromatic nature, these three Aluminum isomers have also strong aromatic regions interspersed with anti-aromatic regions indicating a probable plasmonic character of the present Al 13 + system.…”

Section: Introductionmentioning

confidence: 84%

“…A series of Aluminum chain containing 2 to 9 atoms along with a triangular and a square shaped small clusters have been depicted in Fig. Now the turn to discuss the set of planar and quasi-planar Al 13 + cluster whose optimized structure and electronic character have already been reported by us [19,20]. Among these three clusters one is perfectly planar whereas two other are quasi-planar structures.…”

Section: Optimized Geometry Of Small Al Clustersmentioning

confidence: 90%

Quantifying plasmonic characteristics of a series of pure Aluminum and alkali doped Aluminum clusters

Guin¹,

Jana²

2022

Preprint

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Al clusters have drawn tremendous attention of scientific community for their characteristic deep ultraviolet plasmonic emission. In this study, we have explored the plasmonic characteristics of a series of linear (Aln; n = 2 to 9) and cyclic aluminum clusters (n = 3,4) along with our recently reported three Al13+ isomer system [Guin et. al. Journal of Molecular Graphics and Modeling, 2020, 97, 107544] and corresponding alkali doped clusters [Guin et. al. Journal of Molecular Modeling, 2021, 27, 235]. Among the three Al13+ isomers one is perfectly planar (CI) and two others are quasi-planar clusters (CT and CII). It is a well-known fact that properties of nano-clusters strongly depend on the size and shape of the clusters. The current study reveals that for the linear chains the plamonic character systematically increases with the nuclearity of the clusters. For the cyclic clusters (Al3 and Al4) the plamonicity is lower compared to corresponding linear clusters. In case of Al13+ isomer system, the planar isomer is having higher plasmonicity compared to the non-planar isomers. The doping of alkali atoms in planar clusters, has a general tendency to reduce the plasmonic nature compared to the undoped clusters. The plasmonic emission for these aluminum clusters fall in the UV range (170 to 416 nm).

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Planarity does not always mean higher aromaticity – Intriguing metalloaromaticity of three Al13+ isomers

Cited by 6 publications

References 44 publications

Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Effect of Alkali Atom Doping on the Electronic Structure and Aromatic Character of Planar and Quasi-Planar Al13+ Clusters

Quantifying plasmonic characteristics of a series of pure Aluminum and alkali doped Aluminum clusters

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Planarity does not always mean higher aromaticity – Intriguing metalloaromaticity of three Al13+ isomers

Cited by 6 publications

References 44 publications

Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Carbon-[n]Triangulenes and Sila-[n]Triangulenes: Which Are Planar?

Effect of Alkali Atom Doping on the Electronic Structure and Aromatic Character of Planar and Quasi-Planar Al13+&nbsp;Clusters

Quantifying plasmonic characteristics of a series of pure Aluminum and alkali doped Aluminum clusters

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Effect of Alkali Atom Doping on the Electronic Structure and Aromatic Character of Planar and Quasi-Planar Al13+ Clusters