Spectroscopic and Ab Initio Investigation of C−H⋅⋅⋅N Hydrogen‐Bonded Complexes of Fluorophenylacetylenes: Frequency Shifts and Correlations

Dey, Arghya; Mondal, Sohidul Islam; Sen, Saumik; Patwari, G. Naresh

doi:10.1002/cphc.201600343

Cited by 9 publications

(6 citation statements)

References 49 publications

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“…Moreover, it was also shown that the dispersion energy component modulates the trends observed in total stabilization energy . On the other hand, for a series of ammonia and methylamine complexes of fluorine-substituted phenylacetylenes (PA), the shifts in the acetylenic C–H stretching vibration were linearly correlated with the stabilization energies . For a series of O–H···O hydrogen-bonded water complexes of fluorophenols, based on the correlation between the shifts in the O–H stretching frequencies and the stabilization energies, the complexes were categorized into two sets.…”

Section: Introductionmentioning

confidence: 99%

“…35 On the other hand, for a series of ammonia and methylamine complexes of fluorine-substituted phenylacetylenes (PA), the shifts in the acetylenic C−H stretching vibration were linearly correlated with the stabilization energies. 36 For a series of O−H•••O hydrogen-bonded water complexes of fluorophenols, based on the correlation between the shifts in the O−H stretching frequencies and the stabilization energies, the complexes were categorized into two sets. However, the energy decomposition analysis (EDA) revealed that the shifts in the O−H stretching frequencies were linearly correlated with the electrostatic component of the stabilization energy.…”

Section: ■ Introductionmentioning

confidence: 99%

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Electrostatics and Dispersion in X–H···Y (X = C, N, O; Y = N, O) Hydrogen Bonds and Their Role in X–H Vibrational Frequency Shifts

Sen

Patwari

2018

ACS Omega

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The frequency shifts of donor stretching vibration in X–H···Y (X = C, N, O; Y = N, O) hydrogen-bonded complexes of phenylacetylene, indole, and phenol are linearly correlated with the electrostatic component of the interaction energy. This linear correlation suggests that the electrostatic component, which is the first-order perturbative correction to the stabilization energy, is essentially localized on the X–H group. The linear correlation suggests that the electrostatic tuning rate, which is a measure of the X–H oscillator to undergo shifts upon hydrogen bonding per unit increase in the electrostatic component of the stabilization energy, was found to be in the order of O–H > N–H > C–H. Interestingly, for each of the donor groups, viz., C–H, N–H, and O–H, the vibrational frequency shifts were inversely correlated to the dipole moment of the acceptor separately, which is counterintuitive vis-à-vis the electrostatic component. This implies that extrapolation to zero dipole moment of the acceptor will yield very large shifts in the hydrogen-bonded X–H stretching frequencies. The trends in the variation of the dispersion and exchange-repulsion components and the total interaction energy vis-à-vis frequency shifts of donor stretching vibration are similar for hydrogen-bonded complexes of phenylacetylene, indole, and phenol. Furthermore, it was observed that the vibrational frequency shifts of all of the complexes are linearly correlated with the charge transfer from the filled orbital of the hydrogen acceptor to the vacant antibonding (σ*) orbital of the X–H donor group on the basis of natural bonding orbital calculations.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Electrostatics and Dispersion in X–H···Y (X = C, N, O; Y = N, O) Hydrogen Bonds and Their Role in X–H Vibrational Frequency Shifts

Sen

Patwari

2018

ACS Omega

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“…There have been many works on the issue of two types of frequency shifts reporting a large number of correlations of various quantities with the objective of rationalising or predicting whether there will be red or blue shift. However, the issue is still not resolved and there are many attempts to provide further insight through several calculations [11][12][13][14][15][16][17][18][19][20][21][22][23][24] and experimental investigations. [24][25][26][27][28] There is thus no single model or explanation that can definitely point out whether a hydrogen bond will show blue shift or red shift in its stable configuration.…”

Section: Introductionmentioning

confidence: 99%

A computational investigation of the red and blue shifts in hydrogen bonded systems

Das

Ghosh

2017

J Chem Sci

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The present work reports results of computational investigations of hydrogen bonding, with regard to the most common red shift in the vibrational frequency, as well as the less common blue shift in several hydrogen bonded systems. A few new correlations of the frequency shifts with the calculated electrostatic parameters are proposed, thereby generating new insight into both types of the frequency shifts. Thus, the frequency shifts in X-H--Y hydrogen bonded systems at different H-Y distances are shown to correlate well with the Mulliken charges on H and Y, with the positive and negative charges on Y correlating with the blue and red shift of the frequency of X-H vibration, respectively. The role played by charge transfers at other parts of the interacting system is also discussed.

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“…The IR spectra in the acetylenic CÀ H stretching region of all the MA complexes were recorded using the IR-UV double resonance spectroscopic method and are presented in Figure S1 (see the Supporting Information, SI). [9,12] Further, IR-UV hole-burning spectra were recorded, whenever required, to sort out multiple bands observed in Figure 1. The structures of the MA complexes were assigned based on the observed IR spectra with aid of highlevel ab-initio calculations at MP2/aug-cc-pVDZ//CCSD(T)/CBS level of theory and Figure 2 shows the structures of all the MA complexes responsible for spectra presented in Figure 1 ).…”

Section: Resultsmentioning

confidence: 99%

Hydrogen‐Bonded Complexes of Fluorophenylacetylenes: To Fluoresce or Not?

2020

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The hydrogen‐bonded complexes of fluorophenylacetylenesexhibit unusual and interesting fluorescence turn ON/OFF behaviour following excitation to 1ππ* (S1) state. The fluorescence switching behaviour can be realized by (i) “change in the intermolecular structure, (ii) change in the position of fluorine substitution and (iii) change in the hydrogen bonding partner or a combination thereof. Experiments indicate that the ≡C−H⋅⋅⋅X (X=O, N) hydrogen bonding with the acetylenic group plays a pivotal role in this switching behaviour. Intriguingly, weaker ≡C−H⋅⋅⋅X hydrogen bonding leads to fluorescence OFF state, which is turned ON by stronger hydrogen bonding. The observed fluorescence this switching behaviour is rationalized on the basis of a phenomenological model which suggests a coupling between the initially excited S1 state and a dark Sn state in the Franck‐Condon region with limited window controlled by the ≡C−H⋅⋅⋅X hydrogen bonding as a crucial parameter. Such fluorescence switching behaviour in hydrogen‐bonded complexes is unprecedented and these intriguing results hopefully will stimulate theoreticians to test ′state of the art′ theories to explain these observations in a consistent manner.

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Spectroscopic and Ab Initio Investigation of C−H⋅⋅⋅N Hydrogen‐Bonded Complexes of Fluorophenylacetylenes: Frequency Shifts and Correlations

Cited by 9 publications

References 49 publications

Electrostatics and Dispersion in X–H···Y (X = C, N, O; Y = N, O) Hydrogen Bonds and Their Role in X–H Vibrational Frequency Shifts

Electrostatics and Dispersion in X–H···Y (X = C, N, O; Y = N, O) Hydrogen Bonds and Their Role in X–H Vibrational Frequency Shifts

A computational investigation of the red and blue shifts in hydrogen bonded systems

Hydrogen‐Bonded Complexes of Fluorophenylacetylenes: To Fluoresce or Not?

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