Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and <i>ab initio</i> study

Yang, Yu Min; Li, Chen; Yin, Bing; Li, Jianli; Huang, Yuanhe; Wen, Zhenhai; Jiang, Zhenyi

doi:10.1063/1.4817189

Cited by 39 publications

(19 citation statements)

References 91 publications

(128 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Polynuclear superhalogens (M n X n · k + 1 ), of which the number of central atoms ( n ) is larger than one, take advantage of increasing the number of ligands while maintaining their high stability and, therefore, exploring polynuclear superhalogens has become an essential novel research direction (see Refs. and references cited therein). Examples include magnesia halogens whose electron affinities do not only confirm their superhalogen nature but also reveal a strong relationship with the number of central metal atoms.…”

Section: Introductionmentioning

confidence: 99%

Mg₃F₇: A superhalogen with potential for new nanomaterials design

Sikorska

2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The stability of the Mg3F7 cluster and its ability to ionize nanoparticles has been investigated theoretically. At the CCSD(T) level of theory, the Mg3F7 cluster has been confirmed to be superhalogen due to its high adiabatic electron affinity (7.9 eV). The corresponding daughter anionic species (Mg3F7−) displays a highly symmetric (C3v) umbrella‐like structure and magic cluster stability. The extra electron of the Mg3F7− anion aggregates on the terminal fluorine ligands with non‐negligible distribution occurring on the bridging F units too. These two properties lower both the kinetic and potential energies of the extra electron respectively and thus lead to large electron binding energy. When interacting with the fullerene nanoparticle (C60), the radical neutral Mg3F7 superhalogen captures an electron and forms stable and strongly bound “binary salts” consisted of Mg3F7− anion and C60•+ radical cation. Thus, Mg3F7 can be used as an effective oxidizing agent to construct new ionized nanomaterials.

show abstract

Section: Introductionmentioning

confidence: 99%

Mg₃F₇: A superhalogen with potential for new nanomaterials design

Sikorska

2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

show abstract

“…The utility of superhalogens in the design and synthesis of new materials of technological importance has spurred considerable interest not only in expanding their scope but also in finding ways to enhance their electron affinities. Recent works have shown that superhalogens are not restricted to just a metal atom at the core surrounded by halogen atoms but can be created when the core atom is replaced by a cluster, when the ligands are no longer halogen atoms, and even when none of the constituents are metal or halogen atoms . Equally important, a new class of electronegative clusters called hyperhalogens has emerged where the halogen ligands are replaced by superhalogen ligands, enabling their electron affinities to surpass those of their superhalogen building blocks.…”

Section: Introductionmentioning

confidence: 99%

Electron affinity of modified benzene

Driver

Jena

2017

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The electron affinities of organic molecules obeying H€ uckel's rule of aromaticity are vanishingly small, if not negative. For example, benzene, a classic example of an aromatic molecule, has an electron affinity of 21.15 eV. Using density functional theory, we have systematically calculated the electron affinities and vertical detachment energies of C 6 H 6 by substituting H with halogen (F) and superhalogen (BO 2 ) moieties, as well as replacing one of the C atoms with B. The ground state geometries were obtained by examining about 330 isomers. The electron affinities are found to steadily increase with these substitutions/replacements, even surpassing that of Cl, the element with the highest electron affinity in the periodic table, in the case of C 5 BH(BO 2 ) 5 . In some special cases such as C 6 H 5 (BO 2 ) the electron affinity and vertical detachment energy differ by as much as 5 eV, indicating substantial changes in the geometry as the electron is removed from the anion.We hope that the ability to change the negative electron affinity of C 6 H 6 to large positive values by substituting H and/or replacing C atom will motivate experimental studies.benzene, electron affinity, H€ uckel's rule, superhalogen 1 | I N TR ODU C TI ON Negative ions play an important role in chemistry as strong oxidizing agents. Among all elements in the periodic table, halogens readily form negative ions with F being the most electronegative element and Cl having the highest electron affinity, namely 3.6 eV, among elements in the periodic table. More than half a century ago, a new chapter in negative ion chemistry opened when Bartlett and coworkers [1,2] discovered that the O 2 molecule, as well as the Xe atom can be oxidized by PtF 6 . The authors estimated the electron affinity of PtF 6 to be in excess of 6.76 eV. In the early 1980s, Boldyrev and Gutsev [3][4][5][6] coined the word superhalogen to describe the properties of molecules like PtF 6 . They showed that a cluster containing a metal atom, M, of valence k at the core and decorated with (k 1 1) number of halogen, X, atoms would have electron affinities that are larger than that of the halogen atom they are composed of. Thus, MX (k11) would constitute a class of clusters that mimics the chemistry of halogen atoms. Because their electron affinities are larger than those of halogen atoms, superhalogens can also form chemical bonds with atoms having rather high ionization potentials. That XePtF 6 could form in spite of the large ionization potential of Xe, namely 12.2 eV, [7] bears testimony to the unusual chemistry of superhalogens. In addition to allowing noble gases to participate in new chemistry, [8] superhalogens have been recently found to lead to a new generation of electrolytes in Li ion batteries [9][10][11][12] and hybrid perovskite-based solar cells. [13,14] The utility of superhalogens in the design and synthesis of new materials of technological importance has spurred considerable interest not only in expanding their scope but also in finding ways to enhance the...

show abstract

“…H. Yang et al designed hetero‐binuclear superhalogen anions with cyanides and isocyanides as ligands . We have also found that there are several superhalogens are available in the literature such as binuclear, trinuclear and polynuclear superhalogens, iron‐based magnetic superhalogens, antiferromagnetic binary hyperhalogen, novel superhalogens with metal oxyfluoride ligands, traditional halogen based superhalogens and N5‐based aromatic hyperhalogen anions . The application of superhalogens are also manifold.…”

Section: Introductionmentioning

confidence: 80%

Superhalogens as Building Blocks of Super Lewis Acids

et al. 2019

View full text Add to dashboard Cite

Lewis acids play an important role in synthetic chemistry. Using first‐principle calculations on some newly designed molecules containing boron and organic heterocyclic superhalogen ligands, we show that the acid strength depends on the charge of the central atom as well as on the ligands attached to it. In particular, the strength of the Lewis acid increases with increasing electron withdrawing power of the ligand. With this insight, we highlight the importance of superhalogen‐based ligands in the design of strong Lewis acids. Calculated fluoride ion affinity (FIA) values of B[C2BNO(CN)3]3 and B[C2BNS(CN)3]3 show that these are super Lewis acids.

show abstract

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study

Cited by 39 publications

References 91 publications

Mg₃F₇: A superhalogen with potential for new nanomaterials design

Mg₃F₇: A superhalogen with potential for new nanomaterials design

Electron affinity of modified benzene

Superhalogens as Building Blocks of Super Lewis Acids

Contact Info

Product

Resources

About

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study

Cited by 39 publications

References 91 publications

Mg3F7: A superhalogen with potential for new nanomaterials design

Mg3F7: A superhalogen with potential for new nanomaterials design

Electron affinity of modified benzene

Superhalogens as Building Blocks of Super Lewis Acids

Contact Info

Product

Resources

About

Mg₃F₇: A superhalogen with potential for new nanomaterials design

Mg₃F₇: A superhalogen with potential for new nanomaterials design