DFT study of alkali and alkaline earth metal-doped benzocryptand with remarkable NLO properties

Maqsood, Nimra; Asif, Areeba; Ayub, Khurshid; Iqbal, Javed; Elnaggar, Ashraf Y.; Mersal, Gaber A.M.; Ibrahim, Mohamed M.; El‐Bahy, Salah M.

doi:10.1039/d2ra02209e

Cited by 23 publications

(12 citation statements)

References 55 publications

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“…Lower the E gap , higher will be the softness and polarizability of the compound which yields high reactivity. 65 Table S25 † reveals that among all derivatives, PMDC7 exhibits highest (0.0488 E h ) value of hardness while, PMDC6 shows lowest value (0.0368 E h ). The decreasing order of hardness is: PMDC7 > PMDC8 > PMD-1 > PMDC3 > PMDC2 > PMDC4 > PMDC5 > PMDC6.…”

Section: Resultsmentioning

confidence: 99%

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

et al. 2022

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Section: Resultsmentioning

confidence: 99%

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

et al. 2022

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“…The electron density difference map (EDDM) analysis was accomplished to comprehend the subsequent charge density present on the compounds and the reorganization of electrons after charge transfer [63]. It also delivers information about the distribution of electrons after transition from ground to excited state [17] and provides visualization of the difference of electron density that is, charge density present on the excited‐state molecular orbitals subtracted from the ground state molecular orbitals ( ρ excited − ρ ground ) [37]. So, the EDDM of cage and all the designed complexes were computationally simulated at ωB97XD/6–31 + G (d, p) level of theory and have been visualized in Figure 6.…”

Section: Resultsmentioning

confidence: 99%

“…transition from ground to excited state [17] and provides visualization of the difference of electron density that is, charge density present on the excited-state molecular orbitals subtracted from the ground state molecular orbitals (ρ excited À ρ ground ) [37]. So, the EDDM of cage and all the designed complexes were computationally simulated at ωB97XD/6-31 + G (d, p) level of theory and have been visualized in Figure 6.…”

Section: F I G U R Ementioning

confidence: 99%

“…Electrides [36] and alkalides [37] are better representatives of the family of excess electrons compounds because of the their extraordinary NLO response [38]. A large number of electrides and alkalides are theoretically designed by doping of metal atom on diverse complexants such as cyclacene fluorocarbons, calix [4]pyrrole, cyclic polyamines, 3 6 Adz, 15-crown-5 and 12-crown-4 [39][40][41][42][43][44], and so forth.…”

Section: Introductionmentioning

confidence: 99%

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DFT study of enhancement in nonlinear optical response of exohedrally and endohedrally alkaline earth metals (Be, Mg, Ca) doped adamanzane

Rafique

Maqbool

Shehzad

et al. 2022

Int J of Quantum Chemistry

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In this study, density functional theory has been used to investigate the geometric, electronic, linear and nonlinear optical properties of exohedrally and endohedrally doped adamanzane M1(26 adz)M2 where (M1 = M2 = Be, Mg and Ca). The multiple doping rendered excess electrons to the system which resulted in increased HOMO energies and resultantly reduced HOMO‐LUMO gap (from 8.85 eV to 4.87 eV). The significant changes in excitation energy and vertical ionization energy indicated the introduction of excess electrons to the system. The NBO analysis confirmed that both the dopants are electron donating moieties. The formation of new HOMOs were also evident from the density of state (DOS) analysis. The new complexes exhibited remarkable nonlinear optical response and maximum first hyperpolarizability (β = 8.19 × 103 au) and second hyperpolarizability (γ = 8.12 × 105 au) were observed for AM9. This nonlinear response enhanced significantly when materials were placed in the light of 1907 nm wavelength for determination of dynamic hyperpolarizabilities. The UV–Vis analysis confirmed the transparency of designed materials in deep UV region. The structural properties of new materials were also authenticated by IR‐spectra. The exceptionally high nonlinear response makes these materials desirable candidates for photonic, telecommunication and laser applications.

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“…To obtain a deeper understanding of the binding of ions to the [2.2.2]cryptand cage, we substitute a phenyl ring in place of one of the central ethyl groups, forming [2.2.2]benzocryptand , (Figure b). This substitution provides an ultraviolet chromophore that will report on its ionic contents through its electronic spectrum.…”

Section: Introductionmentioning

confidence: 99%

Molecular Cage Reports on Its Contents: Spectroscopic Signatures of Cryo-Cooled K⁺- and Ba²⁺-Benzocryptand Complexes

Foley

Allen

et al. 2023

J. Phys. Chem. A

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UV photofragment spectroscopy and IR–UV double resonance methods are used to determine the structure and spectroscopic responses of a three-dimensional [2.2.2]-benzocryptand cage to the incorporation of a single K+ or Ba2+ imbedded inside it (labeled as K+-BzCrypt, Ba2+-BzCrypt). We studied the isolated ion-cryptand complex under cryo-cooled conditions, brought into the gas phase by nano-electrospray ionization. Incorporation of a phenyl ring in place of the central ethyl group in one of the three N-CH2-CH2-O-CH2-CH2-O-CH2-CH2-N chains provides a UV chromophore whose S0–S1 transition we probe. K+-BzCrypt and Ba2+-BzCrypt have their S0–S1 origin transitions at 35,925 and 36,446 cm–1, respectively, blue-shifted by 174 and 695 cm–1 from that of 1,2-dimethoxybenzene. These origins are used to excite a single conformation of each complex selectively and record their IR spectra using IR–UV dip spectroscopy. The alkyl CH stretch region (2800–3000 cm–1) is surprisingly sensitive to the presence and nature of the encapsulated ion. We carried out an exhaustive conformational search of cage conformations for K+-BzCrypt and Ba2+-BzCrypt, identifying two conformations (A and B) that lie below all others in energy. We extend our local mode anharmonic model of the CH stretch region to these strongly bound ion-cage complexes to predict conformation-specific alkyl CH stretch spectra, obtaining quantitative agreement with experiment for conformer A, the gas-phase global minimum. The large electrostatic effect of the charge on the O- and N-lone pairs affects the local mode frequencies of the CH2 groups adjacent to these atoms. The localized CH2 scissors modes are pushed up in frequency by the adjacent O/N-atoms so that their overtones have little effect on the alkyl CH stretch region. However, the localized CH2 wags are nearly degenerate and strongly coupled to one another, producing an array of delocalized wag normal modes, whose highest frequency members reach up above 1400 cm–1. As such, their overtones mix significantly with the CH stretch modes, most notably involving the CH2 symmetric stretch fundamentals of the central ethyl groups in the all-alkyl chains and the CH stretches adjacent to the N-atoms and antiperiplanar to the nitrogen lone pair.

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DFT study of alkali and alkaline earth metal-doped benzocryptand with remarkable NLO properties

Abstract: Strategies for designing remarkable nonlinear optical materials using excess electron compounds are well recognized in literature to enhance the applications of these compounds in nonlinear optics.

Cited by 23 publications

References 55 publications

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

DFT study of enhancement in nonlinear optical response of exohedrally and endohedrally alkaline earth metals (Be, Mg, Ca) doped adamanzane

Molecular Cage Reports on Its Contents: Spectroscopic Signatures of Cryo-Cooled K⁺- and Ba²⁺-Benzocryptand Complexes

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DFT study of alkali and alkaline earth metal-doped benzocryptand with remarkable NLO properties

Abstract: Strategies for designing remarkable nonlinear optical materials using excess electron compounds are well recognized in literature to enhance the applications of these compounds in nonlinear optics.

Cited by 23 publications

References 55 publications

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

DFT study of enhancement in nonlinear optical response of exohedrally and endohedrally alkaline earth metals (Be, Mg, Ca) doped adamanzane

Molecular Cage Reports on Its Contents: Spectroscopic Signatures of Cryo-Cooled K+- and Ba2+-Benzocryptand Complexes

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Molecular Cage Reports on Its Contents: Spectroscopic Signatures of Cryo-Cooled K⁺- and Ba²⁺-Benzocryptand Complexes