Fluxional bonds in quasi‐planar  and half‐sandwich  (M = K, Rb, and Cs)

Yan, Miao; Li, Hairu; Tian, Xinxin; Mu, Yue‐Wen; Lu, Hai‐Gang; Li, Si‐Dian

doi:10.1002/jcc.25782

Cited by 10 publications

(3 citation statements)

References 49 publications

(84 reference statements)

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“…A negligible rotational barrier was found (0.1 kcal·mol –1 ), and the BO-MD simulations confirmed the rotation of the inner B 6 unit inside the perimeter of the B 12 ring. Very recently, Yan et al showed that the fluxional character of B 18 2– is retained in the presence of an M + counterion (M = K, Rb, Cs) …”

Section: The Gear To the Wankel Rotor Familymentioning

confidence: 99%

Fluxional Boron Clusters: From Theory to Reality

et al. 2019

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Section: The Gear To the Wankel Rotor Familymentioning

confidence: 99%

Fluxional Boron Clusters: From Theory to Reality

et al. 2019

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“…In addition, as ligands involve in cluster formation, they do not simply attach to the surface of clusters but deeply incorporate into the metal core and change its geometric and electronic structure. This adds complexity and eliminates the possibility of planer and delocalized bond clusters [7,8]. Recently, ab initio studies have found silver lead species stabilized by p-d hybridization [9].…”

Section: Introductionmentioning

confidence: 99%

Electrical devices designed based on inorganic clusters

Hu¹,

Yan²,

Zhang³

et al. 2022

Nanotechnology

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The idea of exploring at bottom brink of material science has been carried out for more than two decades. Clusters science is the frontmost studies among all nanoscale structures. Being an example of 0-dimensional quantum dot, nanocluster is serving as the bridge between atomic and conventionally understood solid-state physics. It has been discovered that the forming mechanism of clusters is the parallel effects of electronic and geometric configuration. It is found that electronic shell structure is influencing the properties and geometric structure of the cluster until its size becomes larger where electronic effects submerge in geometric structure. The discrete electronic structures are dependent on the size and conformation of clusters, which can be controlled artificially for the potential device applications. Especially, small clusters with a size of 1-2 nm, whose electronic states are possibly discrete enough to overcome thermal fluctuations, are expected to build single-electron transistor with room-temperature operating. However, exciting as the progress may be seen, the clusters science still falls within the territory of merely the extension of atomic and molecular science. Its production rate limits the scientific and potential application researches of nanoclusters. It is suggested in this review that the mass-produce ability without losing the atomic precision selectivity would be the milestone for nanoclusters to advance to the material science.

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“…Our investigation profits from experience of our previous studies on fluxional molecules and fluxional bonds. [6][7][8][9][10][11][12][13] We note that an even more drastic restriction of bullvalene's isomerizations to just one isomerization of two equivalent isomers has been achieved by replacing the three CH groups of the "wheel" ABC of C 10 H 10 shown in Figure 1 by just two or even by just a single CH group. These modifications generate the so-called barbaralane and semi-bullvalene (SBV) which have lent themselves to enormous numbers of illuminating experimental and theoretical investigations.…”

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confidence: 99%

Restriction on molecular fluxionality by substitution: A case study for the 1,10‐dicyanobullvalene

Pei,

Yang,

Gao

et al. 2024

J Comput Chem

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We show herein that 1,10‐dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10‐dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born‐Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long‐time limit, isomerizations of the 14 isomers, each with Cs symmetry, approach the “14 Cs → C7v” thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C7v symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un‐explored properties e.g. for the equilibration dynamics of C10H10.

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Fluxional bonds in quasi‐planar and half‐sandwich (M = K, Rb, and Cs)

Cited by 10 publications

References 49 publications

Fluxional Boron Clusters: From Theory to Reality

Fluxional Boron Clusters: From Theory to Reality

Electrical devices designed based on inorganic clusters

Restriction on molecular fluxionality by substitution: A case study for the 1,10‐dicyanobullvalene

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