Intramolecular H···H Interactions for the Crystal Structures of [4-((<i>E</i>)-But-1-enyl)-2,6-dimethoxyphenyl]pyridine-3-carboxylate and [4-((<i>E</i>)-Pent-1-enyl)-2,6-dimethoxyphenyl]pyridine-3-carboxylate; DFT Calculations on Modeled Styrene Derivatives

Grabowski, Sławomir J.; Pfitzner, Arno; Zabel, Manfred; Dubis, Alina T.; Palusiak, Marcin

doi:10.1021/jp0351829

Cited by 71 publications

(36 citation statements)

References 42 publications

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“…Further Valence Bond studies have revealed [78], in line with our conclusions, that, apart from the crucial dispersion term, also the σ/σ*(C-H) polarization/charge transfer and electrostatic contributions are important. Recently, numerous reports are present in the literature on the stabilizing nature of CH¨¨¨HC interactions in various types of hydrocarbons [37,38,[79][80][81][82][83][84][85], as well as their importance in catalysis [42,43,86].…”

Section: Resultsmentioning

confidence: 99%

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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Abstract:In the present work, an in-depth, qualitative and quantitative description of non-covalent interactions in the hydrogen storage materials LiN(CH 3 ) 2 BH 3 and KN(CH 3 ) 2 BH 3 was performed by means of the charge and energy decomposition method (ETS-NOCV) as well as the Interacting Quantum Atoms (IQA) approach. It was determined that both crystals are stabilized by electrostatically dominated intra-and intermolecular M¨¨¨H-B interactions (M = Li, K). For LiN(CH 3 ) 2 BH 3 the intramolecular charge transfer appeared (B-HÑLi) to be more pronounced compared with the corresponding intermolecular contribution. We clarified for the first time, based on the ETS-NOCV and IQA methods, that homopolar BH¨¨¨HB interactions in LiN(CH 3 ) 2 BH 3 can be considered as destabilizing (due to the dominance of repulsion caused by negatively charged borane units), despite the fact that some charge delocalization within BH¨¨¨HB contacts is enforced (which explains H¨¨¨H bond critical points found from the QTAIM method). Interestingly, quite similar (to BH¨¨¨HB) intermolecular homopolar dihydrogen bonds CH¨¨¨HC appared to significantly stabilize both crystals-the ETS-NOCV scheme allowed us to conclude that CH¨¨¨HC interactions are dispersion dominated, however, the electrostatic and σ/σ*(C-H) charge transfer contributions are also important. These interactions appeared to be more pronounced in KN(CH 3 ) 2 BH 3 compared with LiN(CH 3 ) 2 BH 3 .

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Section: Resultsmentioning

confidence: 99%

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

2016

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“…There is at present considerable interest in the experimental and theoretical studies of hydrogen bonding effects on the conformation and stability of organic molecules 31–37…”

Section: Resultsmentioning

confidence: 99%

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

Schaming

Xia

Thouvenot

2012

Chemistry A European J

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An electrosynthesis process has allowed the formation of four oligomers, containing three, four, or five macrocycles. This method is based on the nucleophilic attack of porphyrins substituted by several pendant pyridyl groups to the electrogenerated radical cation of zinc β-octaethylporphyrin (ZnOEP), according to an ECEC processes. Thus, a control of the number of macrocycles and of the geometry of the oligomers can be performed. These new compounds have been characterized by HRMS as well as (1)H NMR, UV/Vis, and fluorescence spectroscopy, and electrochemistry. The results show a strong influence of the pyridinium spacers on the macrocycles.

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“…The quantum theory of atoms in molecules of Bader 22 has been utilized to explore various interactions in a molecular system and its ability to identify these interactions between inter-atomic regions in terms of bond critical points and the formation of ring surfaces characterized by ring critical points is well documented. [51][52][53][54] Examples of molecular graphs generated from the QTAIM analysis are show in Values of ρ BCP < 0.10 au are indicative of a closed-shell (i.e., predominantly non-covalent) interaction; 55 it is usually accompanied by a relatively small and positive value of  2 ρ BCP . 56 By contrast, for a shared (i.e., predominantly covalent) interaction, ρ BCP is usually > 0.1 au 55 (or > 0.15 au 57 ) and  2 ρ BCP , which may be positive or negative 55 (but usually negative 57 ), is typically of the same order as ρ BCP .…”

Section: Resultsmentioning

confidence: 99%

A Density Functional Theory- and Atoms in Molecules-based Study of NiNTA and NiNTPA Complexes toward Physical Properties Controlling their Stability. A New Method of Computing a Formation Constant

Cukrowski

Govender

2010

Inorg. Chem.

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The log K 1 value of analytical quality was obtained for the NiNTPA complex using the DFTcomputed (at the B3LYP/6-311++G(d,p) level of theory in solvent, CPCM/UAKS) G (aq) values of the lowest energy conformers of the ligands, NTA (nitrilotriacetic acid) and NTPA (nitrilotri-3-propanoic acid), and Ni(II) complexes (NiNTA and NiNTPA). The described mathematical protocol is of general nature. The topological analysis, based on the Quantum Theory of Atoms in Molecules (QTAIM) of Bader, was used to characterize coordination bonds, chelating rings and additional intramolecular interactions in the complexes. The topological data, but not the structural analysis, explained the observed difference in stability of the NiNTA and NiNTPA complexes. It was found that the structural H···H contacts (classically regarded H-clashes, a steric hindrance destabilizing the complex) are in fact the H-H bonds contributing to the overall stability of NiNTPA. Also a CH-O bond was found in NiNTPA. The absence of intramolecular bonds between the atoms that fulfill a distance criterion in NiNTPA is explained by the formation of adjacent intramolecular rings that have larger electron density at the ring critical points when compared with the rings containing these atoms. It is postulated that the strength of a chelating ring (a chelating effect) can be measured by the electron density at the ring critical point. It was found that the strain energy, E s , in the as-in-complex NTPA ligand (E s is significantly lowered by the presence of the intramolecular bonded interactions found by QTAIM) is responsible for the decrease in strength of NiNTPA; the E s ratio (NTPA/NTA) of 1.9 correlates well with the experimental log K 1 ratio (NTA/NTPA) of 1.98.2

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Intramolecular H···H Interactions for the Crystal Structures of [4-((E)-But-1-enyl)-2,6-dimethoxyphenyl]pyridine-3-carboxylate and [4-((E)-Pent-1-enyl)-2,6-dimethoxyphenyl]pyridine-3-carboxylate; DFT Calculations on Modeled Styrene Derivatives

Cited by 71 publications

References 42 publications

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

Non-Covalent Interactions in Hydrogen Storage Materials LiN(CH3)2BH3 and KN(CH3)2BH3

An Original Electrochemical Pathway for the Synthesis of Porphyrin Oligomers

A Density Functional Theory- and Atoms in Molecules-based Study of NiNTA and NiNTPA Complexes toward Physical Properties Controlling their Stability. A New Method of Computing a Formation Constant

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