Determination of dimerization constants of cis- and trans-configured secondary amides using near-infrared spectrometry

Krikorian, Sandrine

doi:10.1021/j100207a029

Cited by 63 publications

(49 citation statements)

References 1 publication

(1 reference statement)

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“…66,67 In contrast to hydrogen-bonding solvents such as dioxane and water, CCl 4 does not disrupt intermolecular amide-amide hydrogen bonding. [68][69][70] For neat Harmonic Frequencies ν j in cm -1 for N-H, CdO, and C-N NMA, a low-resolution IR spectrum is available in the Merck FT-IR atlas. Here one observes IR stretch frequencies for both hydrogen-bonded and terminal NH groups in neat, liquid NMA.…”

Section: Experimental Ir Frequenciesmentioning

confidence: 99%

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Ludwig¹,

Reis²,

Winter³

et al. 1998

J. Phys. Chem. B

111

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Temperature-dependent infrared spectra for liquid N-methylacetamide are calculated by the ab initio quantum cluster equilibrium (QCE) and Gaussian-94 methods and compared with experimental measurements. The calculations are based on standard ab initio self-consistent-field (SCF) methods at the 3-21G levels for five different molecular clusters. The cluster sizes vary from the monomer up to a five-membered linear structure. Strong cooperative effects are found in the molecular clusters and are reflected in the geometries and vibrational spectra for each species. The equilibrium populations of the clusters were calculated for the entire liquid range. At low temperatures the linear pentamer is the dominant species. At higher temperatures these clusters are replaced, primarily, by linear dimers and monomers. The calculated frequencies are in excellent agreement with the temperature behavior found in FT-IR experiments.

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Section: Experimental Ir Frequenciesmentioning

confidence: 99%

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Ludwig¹,

Reis²,

Winter³

et al. 1998

J. Phys. Chem. B

111

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“…1.5 kcal mol −1 per H-bond, large compared to cis-amides such as pyrrolidone or caprolactam, which show dimerization constants ranging 1–5 M −1 in CHCl 3 . [19] Along with phosphonamidates possessing both a stronger hydrogen bond acceptor (P=O vs. C=O) and a stronger hydrogen bond donor (P(O)N–H vs. C(O)N–H) than amides, the non-coplanar arrangement of donor/acceptor and lower directional preference of P=O donors allow the pseudo 6-membered ring to adopt a chair conformation and minimize repulsive secondary interactions (Figure 3b–c). [20] As a result, this dimer deviates from trends noted by Schneider and Sartorius, where each attractive interaction gives −1.88 kcal mol −1 of energy to ΔG, and each repulsive secondary interaction gives +0.74 kcal mol −1 .…”

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confidence: 99%

Facile Synthesis and Properties of 2‐λ⁵‐Phosphaquinolines and 2‐λ⁵‐Phosphaquinolin‐2‐ones

et al. 2015

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Treatment of 2-ethynylanilines with P(OPh)3 gives either 2,2-diphenoxy-2-λ5-phosphaquinolines or 2-phenoxy-2-λ5-phospha-quinolin-2-ones under transition metal-free conditions. This reaction offers unparalleled access to an underexplored heterocycle, which opens study of the fundamental nature of the N=PV double bond and its potential for delocalization within a cyclic π-electron system. This heterocycle can inherently serve as a carbostyril mimic, with application as a bioisostere for pharmaceuticals based on the 2-quinolone scaffold. Additionally, the molecule holds promise as a new fluorophore, as initial screening reveals quantum yields upwards of ~40%, Stokes shifts of 50–150 nm, and emission wavelengths of 380–540 nm. The phosphaquinolin-2-ones possess one of the strongest solution-state dimerization constants for a D-A system (130 M−1) due to the close proximity of a strong acceptor, P=O, and a strong donor, the phosphonamidate N–H, suggesting this class of compounds might hold promise as new hydrogen bonding hosts for optoelectronic sensing of anions and/or small molecules.

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“…Experimental infrared absorption or calorimetric measurements of the standard free energy of binding in chloroform are available for all six combinations of A, U, C, and G pairs (25,26,27,28). It is important to note that the two experimental techniques differ somewhat.…”

Section: Base Pair Stackingmentioning

confidence: 99%

“…∆G°I R : mean of the cited IR absorption measurements (26,27,28). ∆G°c alor : calorimetric measurements (25).…”

Section: Table IImentioning

confidence: 99%

Modeling Molecular Recognition: Theory and Application

Mardis¹,

Luo

David

et al. 2000

Journal of Biomolecular Structure and Dynamics

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Efficient, reliable methods for calculating the binding affinities of noncovalent complexes would allow advances in a variety of areas such as drug discovery and separation science. We have recently described a method that accommodates significant physical detail while remaining fast enough for use in molecular design. This approach uses the predominant states method to compute free energies, an empirical force field, and an implicit solvation model based upon continuum electrostatics. We review applications of this method to systems ranging from small molecules to protein-ligand complexes.

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Determination of dimerization constants of cis- and trans-configured secondary amides using near-infrared spectrometry

Cited by 63 publications

References 1 publication

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Facile Synthesis and Properties of 2‐λ⁵‐Phosphaquinolines and 2‐λ⁵‐Phosphaquinolin‐2‐ones

Modeling Molecular Recognition: Theory and Application

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Determination of dimerization constants of cis- and trans-configured secondary amides using near-infrared spectrometry

Cited by 63 publications

References 1 publication

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Quantum Cluster Equilibrium Theory of Liquids: Temperature Dependence of Hydrogen Bonding in LiquidN-Methylacetamide Studied by IR Spectra

Facile Synthesis and Properties of 2‐λ5‐Phosphaquinolines and 2‐λ5‐Phosphaquinolin‐2‐ones

Modeling Molecular Recognition: Theory and Application

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Facile Synthesis and Properties of 2‐λ⁵‐Phosphaquinolines and 2‐λ⁵‐Phosphaquinolin‐2‐ones