Structural, spectroscopic, physical properties and quantum chemical investigation on bromide salt of 4-dimethylaminopyridine NLO material for optoelectronic applications

Sivaraj, G.; Jayamani, N.; Siva, V.

doi:10.1016/j.molstruc.2020.128242

Cited by 28 publications

(3 citation statements)

References 28 publications

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“…The medium stretching vibrations of C-N in the pyridinium ring are estimated in the range 1685-1580 cm À1 [27]. The strong band at 1640 cm À1 and a shoulder at 1618 cm À1 were attributed to the C-N-H bending vibration [28]. A weak peak at 982 cm À1 was assigned to the C-H out-of-theplane bending vibration.…”

Section: Synthesis and Characterization Of 4-(dimethylamino)pyridiniu...mentioning

confidence: 99%

4-(Dimethylamino)pyridinium chlorosulfonate: A new ionic liquid exhibiting chlorosulfonic acid action as monoprotic Brönsted acid and no sulfonating reagent

Zaharani

Johan

Titinchi

et al. 2022

Journal of Molecular Liquids

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Section: Synthesis and Characterization Of 4-(dimethylamino)pyridiniu...mentioning

confidence: 99%

4-(Dimethylamino)pyridinium chlorosulfonate: A new ionic liquid exhibiting chlorosulfonic acid action as monoprotic Brönsted acid and no sulfonating reagent

Zaharani

Johan

Titinchi

et al. 2022

Journal of Molecular Liquids

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“…4-(Dimethylamino)pyridine (DMAP), a pyridine derivative, has been used in organic synthesis as a nonmetallic catalyst, − in nanotechnology as a capping agent for the preparation of noble metal nanoparticles and chemical sensors − as well as a stabilizer in perovskite solar cells, and in optoelectronics as a building block for the fabrication of novel nonlinear optical materials. − Most of these applications stem from some combination of three of DMAP’s properties: (1) the delocalized electron of the heterocyclic ring, which allows strong π–π interactions between neighboring DMAP molecules or between the molecule and the substrate, (2) the lone electron pair of the endocyclic nitrogen, which can combine with a proton to form 4-(dimethylamino)pyridinium (DMAPH + ) (Figure ), and (3) the exocyclic nitrogen, which partially donates an electron to the aromatic ring, distorting the character of the ring in the process, making it more basic relative to pure pyridine (Figure ). Factors (2) and (3) strongly influence the protonation of DMAP (and therefore its charge).…”

Section: Introductionmentioning

confidence: 99%

Direct Observation of the Potential-Dependent Protonation and Reorientation of 4-(Dimethylamino)pyridine on Gold Electrodes

2023

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The pyridine derivative, 4-(dimethylamino)pyridine (DMAP), is important in a surprisingly wide variety of applications spanning chemical, biological, and technological domains. Empirically, the protonation state of DMAP and how this protonation state is changed with adsorption on a solid surface are known to play a crucial role in many of these applications. However, direct spectroscopic evidence for bias-dependent DMAP (de)protonation at solid/aqueous interfaces is still very limited. Here, we employed surface-specific vibrational sum frequency (VSF) spectroscopy to study the (de)protonation process of DMAP(H + ) on a polycrystalline gold electrode at neutral pH. Because VSF spectroscopy is interface-specific by its symmetry selection rules, its application allows us to distinguish adsorbed molecules from those close to, but not at, the interface and identify their speciation and orientation with respect to the surface normal. We find that the potentialinduced (de)protonation of flat-lying DMAPH + molecules occurs at relatively low potentials but that both species adsorb horizontally on the surface. A horizontal-to-vertical phase transition occurs only at more positive biases. The physical picture these results suggest confirms and extends that inferred previously from electrochemical measurements and offers a general approach for characterizing interface-induced acid/base chemistry and its relation to interfacial molecular structures.

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“…4-(Dimethylamino)pyridine (DMAP), a pyridine derivative, has been used in organic synthesis as a non-metallic catalyst; [1][2][3][4] in nanotechnology as a capping agent for the preparation of noble metal nanoparticles and chemical sensors [5][6][7][8][9][10][11] as well as a stabilizer in perovskite solar cells; 12 and in optoelectronics as a building block for the fabrication of novel nonlinear optical materials. [13][14][15] Most of these applications stem from some combination of three of DMAP's properties: (1) the delocalized electron of the heterocyclic ring, which allows strong π-π interactions between neighboring DMAP molecules or between the molecule and the substrate, (2) the lone electron pair of the endocyclic nitrogen, which can combine with a proton to form 4-(dimethylamino)pyridinium (DMAPH + )(Figure 1), and (3) the exocyclic nitrogen, which partially donates an electron to the aromatic ring, distorting the character of the ring in the process, making it more basic relative to pure pyridine (Figure 1). Factors (2) and (3) strongly influence the protonation of DMAP (and therefore its charge).…”

Section: Introductionmentioning

confidence: 99%

Direct observation of the potential dependent protonation of 4-(Dimethylamino)pyridine on gold electrodes

Gong

Campen

Tong

2023

Preprint

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The pyridine derivative, 4-(dimethylamino)pyridine (DMAP), is important in a surprisingly wide variety of applications spanning chemical, biological and technological domains. Empirically, the protonation state of DMAP and how this protonation state is changed with adsorption on a solid surface, is known to play a crucial role in many of these applications. However, the direct spectroscopic evidence for bias dependent DMAP (de)protonation at solid/aqueous interfaces is still very limited. Here, we employed surface specific vibrational sum frequency (VSF) spectroscopy to study the (de)protonation process of DMAP(H$^{+}$) on a polycrystalline gold electrode at neutral pH. Because VSF is interface specific by its symmetry selection rules, its application allows us to distinguish adsorbed molecules from those close to, but not at, the interface and identify their speciation and orientation with respect to the surface normal. We find that the potential-induced (de)protonation of flat-lying DMAPH$^{+}$ molecules occurs at relatively low potentials but that both species adsorb horizontally on the surface. A horizontal to vertical phase transition occurs only at more positive biases. The physical picture these results suggest confirms and extends that inferred previously from electrochemical measurements and offers a general approach for characterizing interface-induced acid/base chemistry and its relation to interfacial molecular structure.

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Structural, spectroscopic, physical properties and quantum chemical investigation on bromide salt of 4-dimethylaminopyridine NLO material for optoelectronic applications

Cited by 28 publications

References 28 publications

4-(Dimethylamino)pyridinium chlorosulfonate: A new ionic liquid exhibiting chlorosulfonic acid action as monoprotic Brönsted acid and no sulfonating reagent

4-(Dimethylamino)pyridinium chlorosulfonate: A new ionic liquid exhibiting chlorosulfonic acid action as monoprotic Brönsted acid and no sulfonating reagent

Direct Observation of the Potential-Dependent Protonation and Reorientation of 4-(Dimethylamino)pyridine on Gold Electrodes

Direct observation of the potential dependent protonation of 4-(Dimethylamino)pyridine on gold electrodes

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