Ferrocene conjugated donor-π-acceptor malononitrile dimer: Synthesis, theoretical calculations, electrochemical, optical and nonlinear optical studies

Prabu, S. Balasivanandha; David, Éric; Viswanathan, Thamodharan; Jinisha, J.S. Angelin; Malik, Rohan; Maiyelvaganan, K. Rudharachari; Prakash, M.; Palanisami, Nallasamy

doi:10.1016/j.molstruc.2019.127302

Cited by 29 publications

(11 citation statements)

References 52 publications

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“…The electrochemical potentials of second‐order NLO chromophores provide information on the energy of the highest‐occupied molecular orbital (HOMO). From the oxidation potential ( E ox ), the HOMO can be calculated by using the relationship E HOMO =−( E ox +4.4) [52] …”

Section: Resultsmentioning

confidence: 99%

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Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

David

Colombo

Dragonetti

et al. 2021

Chemistry A European J

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As eries of new b-ketoimines containing af errocene moiety and their BF 2 complexes have been synthesized and structurally characterized. The solvatochromism of the b-ketoimines was studied, putting in evidencearedshift with increasing solvent polarity.T his positive solvatochromism can be attributed to am ore polarizede xcited state compared with the grounds tate, due to intramolecular charge transfer( ICT) transitions. The b-ketoimines exhibited weak emission, attributable to the excited-state intramolecular proton transfer( ESIPT) phenomenon. This ESIPT effect is suppressedu ponr estriction of the keto-enaminet automerism, inducedu pon addition of BF 3 •OEt 2 ,w hich afforded the related BF 2 complexes, characterized by an enhancement of the fluorescence through the ICT effect. Both the b-ketoimines and BF 2 complexes exhibited significant aggregation-inducede mission behavior in mixtureso fC H 3 CN/H 2 O, due to restriction of intramolecular rotationint he aggregated state. The frontier molecular orbital levels,g round-and excitedstate dipole moments (m g and m e ), and the origin of electronic absorption spectra were studied by time-dependent DFT calculations. The second-order nonlinearo ptical (NLO) properties were determined by the electric-field-induced secondharmonic generation technique. The mb 1907 values of the bketoimines increased upon the formationo ft he related BF 2 complexes,m ainly due to an enhancement of the groundstate dipole moment. The resultsp resented here reveal that some of these novel compounds are excellent multifunctional candidates for NLO and luminescence applications.

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Section: Resultsmentioning

confidence: 99%

“…From the oxidation potential( E ox ), the HOMO can be calculated by using the relationship E HOMO = À(E ox + +4.4). [52]…”

Section: Electrochemical Studiesmentioning

confidence: 99%

Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

David

Colombo

Dragonetti

et al. 2021

Chemistry A European J

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“…Interestingly, it was investigated that M06 functional had been intended for parametrized significantly non-covalent interactions, excited states of transition metal, bonding phenomena in transition elements, and thermochemistry of organometallics. [26][27][28][29][30][31] Therefore, herein, DFT study of aforesaid transitions metal complexes was performed at M06/6-311G(d,p) functional which was developed by Zhao and Truhlar. [32] All theoretical calculations were carried out with the assistance of Gaussian 09 program package.…”

Section: Crystallographic Structure Determinationmentioning

confidence: 99%

Antibacterial metal complexes of o‐sulfamoylbenzoic acid: Synthesis, characterization, and DFT study

Siddiqui

Khalid

Ashraf

et al. 2021

Applied Organom Chemis

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Herein, antibacterial transition metal complexes of ML 2 type having osulfamoylbenzoic acid as ligand were synthesized from saccharin. All characterization techniques confirmed the syntheses of non-ionic transition metal Mn II (3), Co II (4), Ni II (5), Cu II (6), and Zn II (7) complexes, where monoanionic o-sulfamoylbenzoic acid acts as a weak field ligand. The FT-IR, elemental analysis, and magnetic susceptibility studies suggested octahedral and square pyramidal geometries depending on the nature of metal ions. Biological activity of these complexes was studied by using six bacterial strains.Interestingly, the bacterial strains Escherichia coli and Klebsiella aerogenes were inhibited to the maximum level by 6. Among aforementioned five complexes, 4 and 6 were found in crystalline form. Apart from experimental study, DFT study was also performed for entitled complexes at the M06/6-311G(d,p) level. A comparative investigation was performed for geometrical parameters and vibrational analysis, and an agreement was obtained. Natural bonding orbital investigations expressed larger value of stabilization energy 21 kcal/mol for 3, 4, and 6 while 42 kcal/mol for 5 and 7. Furthermore, global reactivity findings also disclosed higher value of hardness (2.44-3.09 eV) for entitled chromophores, hence, showed more stability. Moreover, frontier molecular orbital This research work is attributed to the late Prof. Hamid Latif Siddiqui.

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“…Most of the electronic transitions are n−π* interligand charge transfer (ILCT), with some metal-to-ligand Fe(t 2g )!π* and ligand-to-metal π!Fe(e g *) (d-d) charge transfer. [83] Also, HOMO!LUMO in 1 and 2 has substantial $50% major contributions to the relatively weak lower energy (LE) and stronger higher energy (HE) bands, that is, S0!S1 and S0!S2 transitions, indicating the ICT. The higher energy bands are mainly π-π* transitions (ILCT) from the cyclopentadienyls to the substituent pyrazole and phenyl moiety, whereas the lowest energy bands are due to ferrocene (Fe(t 2g )!π*) MLCT transition.…”

Section: Computational Studiesmentioning

confidence: 99%

Aggregation induced emission (AIE)‐active N‐arylated ferrocenyl pyrazole‐based push–pull chromophores: Structural, photophysical, theoretical and effect of substitution on second‐order non‐linear optical properties

David

Kamini

Thirumoorthy

et al. 2021

Applied Organom Chemis

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In this study, we report the synthesis and structural characterization of Narylated ferrocenyl pyrazole [Fc-Pz-(CF 3)-C 6 H 5-R] (R = CH 3 , 1; OCH 3 2), where Pz = pyrazole and Fc = ferrocenyl = Fe(η 5-C 5 H 5)(η 5-C 5 H 4) chromophores with D-π-A-π-D system. The solvatochromic behaviour of compounds 1 and 2 was investigated in various solvents from non-polar to polar. When solvent polarity increases, the charge transfer process produces the more polarized excited state, and consequently, positive solvatochromism was observed. The emission performance of the compounds is weak luminescence in CH 3 CN solution but becomes high emissive in a mixture of water/CH 3 CN fraction at (f w) 90%, demonstrating aggregation-induced emission (AIE) characteristics, and the mechanism of AIE has been attributed to restricted intramolecular rotation (RIR) process. The time-resolved fluorescence lifetime studies have been demonstrated in water/ CH 3 CN mixture at 90%, as it shows three relaxation pathways in their fluorescence decay. In addition, density functional theory calculations have been employed to optimize the geometry of the molecules, followed by computation of dipole moment (μ), first hyperpolarizability (β) using various functionals (B3LYP, long-range corrected CAM-B3LYP and LC-BLYP) and frontier molecular orbital levels for understanding the charge transfer, electrochemical and non-linear optical (NLO) properties. The second-order non-linear optical properties were studied by hyper-Rayleigh scattering (HRS) technique using an incident wavelength at 1064 nm. The chromophores exhibited the first hyperpolarizability (β HRS = 38.6 × 10 −30 e.s.u. for 1 and β HRS = 116.8 × 10 −30 e.s. u. for 2) and were found to be 6.8 times greater than that of the reference material, p-nitroaniline (pNA) (β HRS = 17.1 × 10 −30 e.s.u.). Also, compound 2 shows higher NLO effect because the presence of-OCH 3 group makes effective charge transfer process by mesomeric effect (+M).

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Ferrocene conjugated donor-π-acceptor malononitrile dimer: Synthesis, theoretical calculations, electrochemical, optical and nonlinear optical studies

Cited by 29 publications

References 52 publications

Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

Antibacterial metal complexes of o‐sulfamoylbenzoic acid: Synthesis, characterization, and DFT study

Aggregation induced emission (AIE)‐active N‐arylated ferrocenyl pyrazole‐based push–pull chromophores: Structural, photophysical, theoretical and effect of substitution on second‐order non‐linear optical properties

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Ferrocene conjugated donor-π-acceptor malononitrile dimer: Synthesis, theoretical calculations, electrochemical, optical and nonlinear optical studies

Cited by 29 publications

References 52 publications

Novel Ferrocene‐Appended β‐Ketoimines and Related BF2 Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

Novel Ferrocene‐Appended β‐Ketoimines and Related BF2 Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

Antibacterial metal complexes of o‐sulfamoylbenzoic acid: Synthesis, characterization, and DFT study

Aggregation induced emission (AIE)‐active N‐arylated ferrocenyl pyrazole‐based push–pull chromophores: Structural, photophysical, theoretical and effect of substitution on second‐order non‐linear optical properties

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Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties

Novel Ferrocene‐Appended β‐Ketoimines and Related BF₂ Derivatives with Significant Aggregation‐Induced Emission and Second‐Order Nonlinear Optical Properties