Nejvíce citovaný článek - PubMed ID 25066639
The dominant role of chalcogen bonding in the crystal packing of 2D/3D aromatics
A series of 12-phenyl-closo-thiaboranes (12-(4-X-C6H4)-closo-1-SB11H10, where X = OMe (2), X = SMe (3), X = Ph (4), and X = NMe2 (5)) has been prepared. Except for 2, all compounds exhibit a chalcogen bond of thiaborane to the phenyl ring or the neighboring molecule as major supramolecular structural motif. 5, having the strongest (-12.47 kcal/mol) structure-making intermolecular interaction via noncovalent S···π(phenyl) chalcogen bond, was crystallized from different solvents in the form of various solvatopolymorphs. n-Hexane and diethyl ether can be removed from 5 easily upon the formation of a porous material with large cavities (up to 20.5% of the unit cell). This first stable and useful noncovalently bound organic framework material with an ultramicroporous structure exhibits a molecular sieve effect. The selective and repeatable adsorption of CO2 to the material crystallized from n-hexane was explained on the basis of cooperative and consecutive machine-like molecular interactions of quadrupolar CO2 molecule with B-H and amino groups inside rectangular cavities.
- Publikační typ
- časopisecké články MeSH
In this theoretical study, we set out to demonstrate the substitution effect of PEDOT analogues on planarity as an intrinsic indicator for electronic performance. We perform a quantum mechanical (DFT) study of PEDOT and analogous model systems and demonstrate the usefulness of the ωB97X-V functional to simulate chalcogen bonds and other noncovalent interactions. We confirm that the chalcogen bond stabilizes the planar conformation and further visualize its presence via the electrostatic potential surface. In comparison to the prevalent B3LYP, we gain 4-fold savings in computational time and simulate model systems of up to a dodecamer. Implications for design of conductive polymers can be drawn from the results, and an example for self-doped polymers is presented where modulation of the strength of the chalcogen bond plays a significant role.
- Publikační typ
- časopisecké články MeSH
We have performed a hierarchical ab initio benchmark and DFT performance study of D2 Ch•••A- chalcogen bonds (Ch = S, Se; D, A = F, Cl). The ab initio benchmark study is based on a series of ZORA-relativistic quantum chemical methods [HF, MP2, CCSD, CCSD(T)], and all-electron relativistically contracted variants of Karlsruhe basis sets (ZORA-def2-SVP, ZORA-def2-TZVPP, ZORA-def2-QZVPP) with and without diffuse functions. The highest-level ZORA-CCSD(T)/ma-ZORA-def2-QZVPP counterpoise-corrected complexation energies (ΔECPC ) are converged within 1.1-3.4 kcal mol-1 and 1.5-3.1 kcal mol-1 with respect to the method and basis set, respectively. Next, we used the ZORA-CCSD(T)/ma-ZORA-def2-QZVPP (ΔECPC ) as reference data for analyzing the performance of 13 different ZORA-relativistic DFT approaches in combination with the Slater-type QZ4P basis set. We find that the three-best performing functionals are M06-2X, B3LYP, and M06, with mean absolute errors (MAE) of 4.1, 4.2, and 4.3 kcal mol-1 , respectively. The MAE for BLYP-D3(BJ) and PBE amount to 8.5 and 9.3 kcal mol-1 , respectively.
- Klíčová slova
- benchmark study, chalcogen bonds, coupled-cluster, density functional calculations, noncovalent interactions,
- Publikační typ
- časopisecké články MeSH
We have quantum chemically analyzed the structure and stability of archetypal chalcogen-bonded model complexes D2 Ch⋅⋅⋅A- (Ch = O, S, Se, Te; D, A = F, Cl, Br) using relativistic density functional theory at ZORA-M06/QZ4P. Our purpose is twofold: (i) to compute accurate trends in chalcogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA). At odds with the commonly accepted view of chalcogen bonding as a predominantly electrostatic phenomenon, we find that chalcogen bonds, just as hydrogen and halogen bonds, have a significant covalent character stemming from strong HOMO-LUMO interactions. Besides providing significantly to the bond strength, these orbital interactions are also manifested by the structural distortions they induce as well as the associated charge transfer from A- to D2 Ch.
Although 1-Ph-2-X-closo-1,2-C2B10H10 (X = F, Cl, Br, I) derivatives had been computed to have positive values of the heat of formation, it was possible to prepare them. The corresponding solid-state structures were computationally analyzed. Electrostatic potential computations indicated the presence of highly positive σ-holes in the case of heavy halogens. Surprisingly, the halogen•••π interaction formed by the Br atom was found to be more favorable than that of I.
- Klíčová slova
- halogen bond, icosahedral boron cluster, sigma hole,
- MeSH
- halogenace MeSH
- halogeny chemie MeSH
- molekulární konformace MeSH
- molekulární modely MeSH
- sloučeniny boru chemická syntéza chemie MeSH
- techniky syntetické chemie MeSH
- uhlík chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- halogeny MeSH
- sloučeniny boru MeSH
- uhlík MeSH
Chalcogen atoms are a class of substituents capable of generating inner and outer derivatives of boron clusters. It is well known that chalcogenated boron clusters can form strong σ-hole interactions when a chalcogen atom is a part of an icosahedron. This paper studies σ-hole interactions of dicarbaboranes with two exopolyhedral chalcogen atoms bonded to carbon vertices. Specifically, a computational investigation has been carried out on the co-crystal of (1,2-C2B10H10)2Se4•toluene and a single crystal of (1,2-C2B10H10)2Te4.
- Klíčová slova
- co-crystal, heteroborane, sigma hole,
- MeSH
- borany chemie MeSH
- chalkogeny chemie MeSH
- krystalizace MeSH
- molekulární modely MeSH
- statická elektřina MeSH
- termodynamika MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- borany MeSH
- chalkogeny MeSH
