B12(SCN)12–: An Ultrastable Weakly Coordinating Dianion

Fang, Hong; Jena, P.

doi:10.1021/acs.jpcc.7b00669

Cited by 31 publications

(36 citation statements)

References 43 publications

(111 reference statements)

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“…It may work well on some systems, and may be a failure on the other. Counterintuitive examples supporting our argument above can be found elsewhere …”

Section: Resultssupporting

confidence: 77%

“…Counterintuitive examples supporting our argument above can be found elsewhere. [87][88][89][90][91] Following the most simplified definition provided at the beginning of this section, it seems to us that the CH 3 NH 3 PbI 3 conformer (a) in Figure 1 , respectively. Clearly, each of these is significantly smaller than the sum of the van der Waals radii, 3.24 Å , of the I and H atoms (2.04 and 1.20 Å , [92] respectively), satisfying a criterion of IUPAC recommended for a specific kind of noncovalent interaction.…”

Section: Are the I•••h Intermolecular Distances Illustrated Inmentioning

confidence: 98%

“…[e] There is no specific directional preference for van der Waals, since the angle of interaction can, but not limited to, vary between 90 in o-MAPbI 3 in Glazer notation [85a] can be described by ab 1 a -. This is not indifferent from what can be expected for the corresponding system having Pm 3m (cubic) symmetry, which can be described by a 0 b 0 c 0 in Glazer notation.…”

Section: What Causes the Pronounced Octahedral Tilting In O-ch 3 Nh 3mentioning

confidence: 99%

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Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Varadwaj

Yamashita

2017

J Comput Chem

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Methylammonium lead iodide (CH NH PbI ) perovskite compound has produced a remarkable breakthrough in the photovoltaic history of solar cell technology because of its outstanding device-based performance as a light-harvesting semiconductor. Whereas the experimental and theoretical studies of this system in the solid state have been numerously reported in the last 4 years, its fundamental cluster physics is yet to be exploited. To this end, this study has performed theoretical investigations using DFT-M06-2X/ADZP to examine the principal geometrical, electronic, topological, and orbital properties of the CH NH PbI molecular building block. The intermolecular hydrogen bonded interactions examined for the most important conformers of the system are found to be unusually strong, with binding energies lying between -93.53 and -125.11 kcal mol (beyond the covalent limit, -40 kcal mol ), enabling us to classify the underlying interactions as ultra-strong type since their characteristic properties are unidentical with those have already been proposed as very strong, strong, moderate, weak, and van der Waals. Based on this, together with the unusually high charge transfers, strong hyperconjugative interactions, sophisticated topologies of the charge density, and short intermolecular distances of separation, we have characterized the conformers of CH NH PbI as Mulliken inner complexes. The consequences of these, as well as of the ultra-strong interactions, in designing novel functional nanomaterials are outlined. © 2017 Wiley Periodicals, Inc.

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“…It may work well on some systems, and may be a failure on the other. Counterintuitive examples supporting our argument above can be found elsewhere …”

Section: Resultssupporting

confidence: 77%

Section: Are the I•••h Intermolecular Distances Illustrated Inmentioning

confidence: 98%

Section: What Causes the Pronounced Octahedral Tilting In O-ch 3 Nh 3mentioning

confidence: 99%

See 1 more Smart Citation

Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Varadwaj

Yamashita

2017

J Comput Chem

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“…The role of substituents in enhancing the stability of multiply changed molecules in the gas phase has also been studied by replacing H atoms in B 4 H 4 2− and B 6 H 6 2− by F, Cl, CN or BO . Thus, the replacement of core and ligand atoms can not only transform organic molecules with negative electron affinities into superhalogens, but also enable small dianions to be stable in the gas phase …”

Section: Introductionmentioning

confidence: 99%

“…[13,14] Thus, the replacemento fc ore and ligand atoms can not only transform organic moleculesw ith negative electron affinities into superhalogens, but also enables mall dianions to be stable in the gas phase. [15,16] In this paper,w ef ocus on polycyclic aromatic hydrocarbons to determine if the above scheme indeed can succeed in creating organic dianions. We address three questions:F irst, can one transform naphthalene (C 10 H 8 )t oastable dianion by replacing the Ca toms in the core rings with Ba toms and the H atoms with Fo rC N?…”

Section: Introductionmentioning

confidence: 99%

Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

2017

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Using density functional theory, we have carried out a systematic study of the stability and electronic properties of neutral and multiply charged molecules B C X (n=0, 1, 2; X=H, F, CN). Our main objective is to explore if the replacements of core C atoms and/or H atoms in naphthalene (C H ) can enhance the stability of their dianions. Indeed, we find that the dianions of B C (CN) are more stable than their monoanions with energies of 0.61 eV, 0.57 eV, and 1.97 eV for n=0, 1, 2, respectively. In addition, polycyclic aromatic hydrocarbons become stable as dianions only when H atoms are substituted by more electronegative species. Thus, a rational design approach by tailoring composition and ligands can lead to a new class of organic molecules that are capable of carrying multiple charges.

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Stable Tetra‐ and Penta‐Anions in the Gas Phase

Fang

Jena

2019

Angewandte Chemie

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The quest for stable gas-phase anions in highly negative charge states has been ag reat challenge.W hile multiply charged anions are stabilized in solids and liquids by compensating cations and solvation cells,respectively,stable anions containing less than ah undred atoms in the gas phase and capable of carrying charge beyond À3isunknown. Here, we report the discovery of thermodynamically stable tetra-and penta-anions,c ontaining less than 50 and 80 atoms,r espectively,i nt he gas phase.Auniversal model is developed that explains their stability in terms of the synergy between closed shell, high electron affinity,a nd size and predicts new highlycharged anions by using the known charged clusters as building blocks.S ynthesis of these species can open an ew chapter in materials chemistry.The enhanced stability of ac losed shell atom lies in the quantum mechanical interactions between electrons.E lectrons with the same spins tend to avoid each other, thereby reducing the Coulomb repulsion between them. Therefore, ac losed-shell atom, that is,a na tom with every spin being paired, gains extra stability.T he closed-shell model provides agood explanation for the reactivity of atoms that are only an electron away from the closed shell. Fore xample,ahalogen (Group 17) atom with asingle hole tends to form astable core by gaining one electron from another atom having aw eakly bound unpaired electron, such as an alkali (Group 1). In fact, the mono-anionic state of ah alogen is more stable than its neutral state,a ss hown by its positive electron affinity (EA) defined by

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B₁₂(SCN)₁₂^–: An Ultrastable Weakly Coordinating Dianion

Cited by 31 publications

References 43 publications

Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

Stable Tetra‐ and Penta‐Anions in the Gas Phase

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B12(SCN)12–: An Ultrastable Weakly Coordinating Dianion

Cited by 31 publications

References 43 publications

Hybrid organic–inorganic CH3NH3PbI3perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Hybrid organic–inorganic CH3NH3PbI3perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Rational Design of Stable Dianions by Functionalizing Polycyclic Aromatic Hydrocarbons

Stable Tetra‐ and Penta‐Anions in the Gas Phase

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B₁₂(SCN)₁₂^–: An Ultrastable Weakly Coordinating Dianion

Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design

Hybrid organic–inorganic CH₃NH₃PbI₃perovskite building blocks: Revealing ultra‐strong hydrogen bonding and mulliken inner complexes and their implications in materials design