Search results for "bond"
showing 10 items of 3527 documents
Crystal structure of diethyl 2-amino-5-{4-[bis-(4-methyl-phen-yl)amino]-benzamido}-thio-phene-3,4-di-carboxyl-ate.
2019
The title compound forms a head-to-head centrosymmetric dimer, involving a pair of intermolecular N—H⋯O hydrogen bonds. It also forms two intramolecular bonds between its amine and amide and the ester carbonyl groups.
Substituent Effects on the [N−I−N]+ Halogen Bond
2016
We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond re…
Hydrogen Bonding in Amorphous Alkaline Earth Carbonates
2018
Amorphous intermediates play a crucial role during the crystallization of alkaline earth carbonates. We synthesized amorphous carbonates of magnesium, calcium, strontium, and barium from methanolic solution. The local environment of water and the strength of hydrogen bonding in these hydrated modifications were probed with Fourier transform IR spectroscopy,
Reactivity of 4-Aminopyridine with Halogens and Interhalogens : Weak Interactions Supported Networks of 4-Aminopyridine and 4-Aminopyridinium
2019
The reaction of 4-aminopyridine (4-AP) with ICl in a 1:1 molar ratio in CH2Cl2 produced the expected charge-transfer complex [4-NH2-1λ4-C5H4N-1-ICl] (1·ICl) and the ionic species [(4-NH2-1λ4-C5H4N)2-1μ-I+][Cl–] (2·Cl–) in a 2:1 relation, as indicated by 1H NMR spectroscopy in solution. In contrast, only the ionic compound [(4-NH2-1λ4-C5H4N)2-1μ-I+][IBr2–] (2·IBr2–) was observed in the analogous reaction with IBr. The reaction between 4-AP and I2 in a 1:1 molar ratio also afforded two components, one of which was identified as the congeneric cation in [(4-NH2-1λ4-C5H4N)2-1μ-I+][I7–] (2·I7–) that contains a polyiodide anion as a result of transformation in a 1:2 molar ratio between the starti…
Self-assembly mechanism based on charge density topological interaction energies
2017
The packing interactions have been evaluated in the context of the self-assembly mechanism of crystal growth and also for its impacts on the aromaticity of the trimesate anion. The structure of ethylammonium trimesate hydrate (1) measured at 100 K and a charge density model, derived in part from theoretical structures, is reported. Theoretical structure factors were obtained from the geometry-optimized periodic wave function. The trimesic acid portion of 1 is fully deprotonated and participates in a variety hydrogen bonding motifs. Topological analysis of the charge density model reveals the most significant packing interactions and is then compared to a complementary analysis performed by …
IR Bandshapes of Intramolecularly H-Bonded Systems II. 2,4-Dibromophenol
1984
A detailed quantitative study of the IR bandshape of the ϑs(OH) vibration of 2,4-dibromophenol in a series of solvents is presented.A distinct dependence of band positions, shape parameters, correlation functions and correlation times from solvent polarity has been found.The contribution of various shaping mechanisms to the profile is discussed.
Determination of basic strenght of aliphatic amines through ion pair formation in some ionic liquid solutions
2010
To have an evaluation of the basic strength of aliphatic amines in ionic liquid solution, the stability constants relevant to the formation of amine/p-nitrophenol ion pairs were determined in different ionic liquids at 298 K. In particular, aliphatic (pyrrolidinium) and aromatic (imidazolium) ionic liquids were used. Imidazolium ions, bmim(+) and bm(2)im(+), having different hydrogen bond donor abilities were taken into account. Anions were chosen ([BF(4)(-)], [PF(6)(-)], and [NTf(2)(-)]; where NTf(2) = bis(trifluoromethansulfonyl)imide) showing different shape, size, and coordination ability. Several primary, secondary (cyclic or not), and tertiary amines were used to study the effect of a…
The Photocycle of Bacteriophytochrome Is Initiated by Counterclockwise Chromophore Isomerization.
2022
Photoactivation of bacteriophytochrome involves a cis–trans photoisomerization of a biliverdin chromophore, but neither the precise sequence of events nor the direction of the isomerization is known. Here, we used nonadiabatic molecular dynamics simulations on the photosensory protein dimer to resolve the isomerization mechanism in atomic detail. In our simulations the photoisomerization of the D ring occurs in the counterclockwise direction. On a subpicosecond time scale, the photoexcited chromophore adopts a short-lived intermediate with a highly twisted configuration stabilized by an extended hydrogen-bonding network. Within tens of picoseconds, these hydrogen bonds break, allowing the c…
Thiourea Based Tritopic Halogen Bonding Acceptors
2023
Series of thiourea based tritopic receptor molecules were synthesized to be used as building blocks for halogen-bonded assemblies. Here 16 new receptor molecules were synthesized from two different 2,4,6-trialkyl-1,3,5-tris(bromomethyl)benzene starting materials via tris(isothiocyanatomethyl)benzene intermediates. The alkyl substituents in the benzene ring showed to be important for isothiocyanate group formation instead of competing thiocyanate group. The synthesis route allowed us to synthesize the isothiocyanate intermediates and further the receptor molecules without typically used and highly toxic thiophosgene. Synthesized receptor molecules were used to study their halogen bond accept…
Solid‐state NMR Spectroscopy of Iodine(I) Complexes
2023
Solid-state NMR has been applied to a series of Barluenga-type iodine(I) [L-I-L]PF6 (L=pyridine, 4-ethylpyridine, 4-dimethylaminopyridine, isoquinoline) complexes as their hexafluorophosphate salts, as well as their respective non-liquid ligands (L), their precursor silver(I) complexes, and the respective N-methylated pyridinium and quinolinium hexafluorophoshate salts. These results are compared and contrasted to the corresponding solution studies and single-crystal X-ray structures. As the first study of its kind on the solid-state NMR behavior of halogen(I) complexes, practical considerations are also discussed to encourage wider utilization of this technique in the future. peerReviewed