Alkali-metal-supported bismuth polyhedra-principles and theoretical studies

Kirill Yu Monakhov; Gerald Linti; Lando P. Wolters; F. Matthias Bickelhaupt

doi:10.1021/ic200596c

Alkali-metal-supported bismuth polyhedra-principles and theoretical studies

Kirill Yu Monakhov
, Gerald Linti
, Lando P. Wolters
, F. Matthias Bickelhaupt

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi]^2- using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)_nM_2n-4]^4- with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M′@{(RBi) _nM_2n-4}]^3- involving an additional endohedral alkali-metal ion M′. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (N_bond) of the cage molecules [(RBi)_nM _2n+Q]^Q to the number of bismuth atoms (n_Bi), alkali-metal atoms (n_M), and net charge Q as N_bond = n_Bi + n_M - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali- metallobismaspheres with a macroicosahedral arrangement.

Original language	English
Pages (from-to)	5755-5762
Number of pages	8
Journal	Inorganic Chemistry
Volume	50
Issue number	12
DOIs	https://doi.org/10.1021/ic200596c
Publication status	Published - 20 Jun 2011
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic200596c

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@article{ae9c9391667741a78bdfe6b2701de8b3,

title = "Alkali-metal-supported bismuth polyhedra-principles and theoretical studies",

abstract = "We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi]2- using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)nM2n-4]4- with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M′@\{(RBi) nM2n-4\}]3- involving an additional endohedral alkali-metal ion M′. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (Nbond) of the cage molecules [(RBi)nM 2n+Q]Q to the number of bismuth atoms (nBi), alkali-metal atoms (nM), and net charge Q as Nbond = nBi + nM - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali- metallobismaspheres with a macroicosahedral arrangement.",

author = "Monakhov, \{Kirill Yu\} and Gerald Linti and Wolters, \{Lando P.\} and Bickelhaupt, \{F. Matthias\}",

year = "2011",

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doi = "10.1021/ic200596c",

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volume = "50",

pages = "5755--5762",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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T1 - Alkali-metal-supported bismuth polyhedra-principles and theoretical studies

AU - Monakhov, Kirill Yu

AU - Linti, Gerald

AU - Wolters, Lando P.

AU - Bickelhaupt, F. Matthias

PY - 2011/6/20

Y1 - 2011/6/20

N2 - We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi]2- using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)nM2n-4]4- with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M′@{(RBi) nM2n-4}]3- involving an additional endohedral alkali-metal ion M′. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (Nbond) of the cage molecules [(RBi)nM 2n+Q]Q to the number of bismuth atoms (nBi), alkali-metal atoms (nM), and net charge Q as Nbond = nBi + nM - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali- metallobismaspheres with a macroicosahedral arrangement.

AB - We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi]2- using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)nM2n-4]4- with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M′@{(RBi) nM2n-4}]3- involving an additional endohedral alkali-metal ion M′. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (Nbond) of the cage molecules [(RBi)nM 2n+Q]Q to the number of bismuth atoms (nBi), alkali-metal atoms (nM), and net charge Q as Nbond = nBi + nM - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali- metallobismaspheres with a macroicosahedral arrangement.

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U2 - 10.1021/ic200596c

DO - 10.1021/ic200596c

M3 - Article

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SN - 0020-1669

VL - 50

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EP - 5762

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 12

ER -

Alkali-metal-supported bismuth polyhedra-principles and theoretical studies

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