Conformational stability, vibrational assignments of 2,3-dihydroxy benzaldehyde as supported by ab initio, hybrid density functional theory and normal coordinate analysis

Balachandran, V.; Karpagam, V.

doi:10.1016/j.molstruc.2013.01.039

Cited by 7 publications

(6 citation statements)

References 27 publications

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“…S5-S7 (ESI †). The main bands and their assignments according to literature data 54,[59][60][61] and our DFT calculations in free modifiers (Fig. 4 [15][16][17]19,20,52 Bands in the regions 1070-1110 cm À1 and 1240-1300 cm À1 , according to literature data [15][16][17]19,20,52,53,[56][57][58] as well as our DFT calculations, could be assigned quite confidently to aryl-oxygen-Ti stretching vibrations n(C-O-Ti).…”

Section: Binding Structure Of Ligands At the Nanoparticle Surfacesupporting

confidence: 70%

The effect of substituents on the surface modification of anatase nanoparticles with catecholate-type ligands: a combined DFT and experimental study

Savić

Čomor

Nedeljković

et al. 2014

Phys. Chem. Chem. Phys.

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The surface modification of nanocrystalline TiO2 particles (45 Å) with catecholate-type ligands having different electron donating/electron withdrawing substituent groups, specifically 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,4-dihydroxybenzaldehyde and 4-nitrocatechol, was found to alter the optical properties of nanoparticles in a similar way to catechol. The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites and a reduction of the effective band gap, being slightly less pronounced in the case of electron withdrawing substituents. The investigated ligands have the optimal geometry for binding to surface Ti atoms, resulting in ring coordination complexes of the catecholate type (binuclear bidentate binding-bridging) thus restoring six-coordinated octahedral geometry of surface Ti atoms. From the absorption measurements (Benesi-Hildebrand plot), the stability constants in methanol/water = 90/10 solutions at pH 2 in the order of 10(3) M(-1) have been determined. The binding structures were investigated by using FTIR spectroscopy. Thermal stability of CT-complexes was investigated by using TG/DSC/MS analysis. Quantum chemical calculations on model systems using density functional theory (DFT) were performed to obtain the vibrational frequencies of charge transfer complexes, and the calculated values were compared with the experimental data.

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Section: Binding Structure Of Ligands At the Nanoparticle Surfacesupporting

confidence: 70%

The effect of substituents on the surface modification of anatase nanoparticles with catecholate-type ligands: a combined DFT and experimental study

Savić

Čomor

Nedeljković

et al. 2014

Phys. Chem. Chem. Phys.

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“…In general, the CAH vibrations (stretching, in-plane and out-of-plane bending) computed by DFT method show good agreement with experimental observations. The CAH out-of-plane vibration in Raman spectrum at 761 cm À1 and 829, 761 cm À1 in IR spectrum shows good agreement with computed value at 829, 761 cm À1 in DFT (LSDA) method [12].…”

Section: Carbon-hydrogen Vibrationssupporting

confidence: 73%

Conformational stability, vibrational (FT-IR and FT-Raman) spectra and computational analysis of m-trifluoromethyl benzoic acid

Balachandran¹,

Karpagam²,

Santhi

et al. 2015

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…Dihydroxybenzaldehydes have been used in the synthesis of biologically active molecules, and they have been shown to exhibit a synergic effect with commercial antifungal agents. , Somewhat surprisingly, the available information on this type of compound is very scarce. Experimental IR spectra of neat solid 2,3-DHBA and of the compound in solution have been described − but, to the best of our knowledge, no further detailed experimental IR spectroscopy studies have been reported on dihydroxybenzaldehydes. In particular, no data are available regarding the investigation of the higher-energy conformers either of 2,3-DHBA or 2,4-DHBA in matrix isolation conditions.…”

Section: Introductionmentioning

confidence: 99%

Breaking and Formation of Intramolecular Hydrogen Bonds in Dihydroxybenzaldehydes through UV-Induced Conformational Changes in a Low-Temperature Matrix

et al. 2022

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Hydrogen bonding (HB) has been receiving attention from both experimental and theoretical researchers since its discovery in the 1920s due to its impact on many chemical and biological processes. However, despite the large number of investigations conducted on this topic, the nature of the HBs and, in particular, the estimation of intramolecular HB energies are still very active subjects of research. In this context, here we report a matrix isolation infrared spectroscopy study of 2,3-dihydroxybenzaldehyde (2,3-DHBA) and 2,4-dihydroxybenzaldehyde (2,4-DHBA), which contain two [one resonance-assisted HB (RAHB) and one conventional HB] and one (RAHB) intramolecular hydrogen bonds, respectively, in their most stable conformer. After isolation of the compounds in cryogenic (15 K) krypton matrices, ultraviolet irradiation led to the formation of higher-energy conformers (by a 180°rotation of the hydroxyl and aldehyde groups), which implies breaking of the intramolecular HBs initially existing in the isolated species and, in the case of 2,3-DHBA, to the formation of a new intramolecular HB. In this way, we were able to manipulate the structure of the molecules, allowing to characterize a diversity of intramolecular HBs in which the OH groups participate (from strong intramolecular RAHBs to weaker conventional HBs, and also no intramolecular HBs) through the corresponding vibrational signatures. The spectroscopic studies were complemented by natural bond orbital analysis and the molecular tailoring approach method, in order to estimate the relative intramolecular HB energies and explore the substitution effects on HB strength.

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Conformational stability, vibrational assignments of 2,3-dihydroxy benzaldehyde as supported by ab initio, hybrid density functional theory and normal coordinate analysis

Cited by 7 publications

References 27 publications

The effect of substituents on the surface modification of anatase nanoparticles with catecholate-type ligands: a combined DFT and experimental study

The effect of substituents on the surface modification of anatase nanoparticles with catecholate-type ligands: a combined DFT and experimental study

Conformational stability, vibrational (FT-IR and FT-Raman) spectra and computational analysis of m-trifluoromethyl benzoic acid

Breaking and Formation of Intramolecular Hydrogen Bonds in Dihydroxybenzaldehydes through UV-Induced Conformational Changes in a Low-Temperature Matrix

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