The optical properties of Malachite green (Mg) dye were examined experimentally, including absorption, optical energy gab, refractive index, dielectric constant, optical conductivity and emission spectra in various solvents. Additionally, several significant photophysical parameters were evaluated, including the extinction coefficient (ε), the energy yield of fluorescence (Ef), the length of attenuation Λ (λ), oscillator strength (f), quantum yield (Øf), fluorescence lifetime (\({\uptau }_{{\text{f}}}\)), decay rate radiative constant (kr), and the dipole moment (μ) in addition to absorption and emission cross-sections (σa) and (σe) respectively. Time Dependent Density function theory (TD-DFT) computations were used to generate the theoretical absorption spectra of the (Mg) compound. The energy gap (Eg), electron density, and electrostatic potential were also simulated.
Hinweise
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1 Introduction
Malachite green (MG) is an organic chemical that is used in aquaculture as a color and, controversially, as an antibacterial. Traditionally, silk, leather, and paper have been dyed with MG (Culp & Beland 1996; Raducan et al. 2008). The dye's name is merely derived from its likeness in hue; it is not made from the mineral malachite. MG is used in the pigment industry and is categorized as a triarylmethane dye in the dyestuff industry (Alderman 1985). MG technically refers to the chloride salt [C6H5C(C6H4N(CH3)2)2]Cl, however the name is typically used informally and simply refers to the colored cation. Additionally, oxalate salt is sold. The color is unaffected by the anions. The cation's vibrant green hue stems from a robust absorption band located at 621 nm, with an extinction value of 105 M−1 cm−1 (Fischer et al. 2011).
Understanding the photophysical properties of laser dyes is necessary for the design and development of innovative active media for tunable lasers. Both extrinsic factors (solvent effects) and the dye's molecular structure affect these properties. IR spectra and bond length are two techniques that can be used to investigate the dye molecular structure. A solvent can affect a chromophore's absorption and fluorescence bands in two different ways as (Boldrini et al. 2002): the overall effect and the particular solute–solvent interactions that are the focus of this study.
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The general solvent effect is related to various macroscopic features of the solvent, including solvent polarity and solvent polarizability (Ghazy 1999; Hemdan 2023). It is caused by the chromophore's dipole moment being solvated in both its ground and excited states (Ghazy 2005; Mera-Adasme et al. 2022). Solvent polarity is controlled by several parameters that are reported in the literature (Reichardt 1965), such as the Dimroth Reichardt ET (30) parameter(Haak and Engberts 1986), which characterizes the solvent polarizability using the Kamlet–Abboud–Taft (π* scale) and spectroscopic data from solvatochromic dyes, and the Lippert parameter, which is related to the solvent's refractive index and dielectric constant(Asemare et al. 2023; Ghazy 1998; Sıdır & Sıdır, 2013).
The specific solute–solvent interactions between solute and solvent molecules provide the basis for solvatochromic interactions, which depend on the properties of both partners. These comprise interactions between solvents and solutes in the form of H-bonds as well as any other multiplex creation (charge-transfer multiplexes) between solvents and solutes. (Demchenko 2023; Medintz et al. 2009). Due to intramolecular charge transfer (ICT), a single molecule with both substituents that donate electrons (D) and those that absorb electrons (A) displays notable spectral and optical properties (Palion-Gazda et al. 2019; Samanta & Misra 2023). As the polarity of the solvent rises, they exhibit notable redshifts in their emission spectra and changes in their photophysical properties (Khopde et al. 2000; Nath et al. 2022).
Malachite green has drawn an enormous curiosity from researchers over the years due to its biological applications and potential as a toxicological contaminant; however, little research has been done on the malachite green optical and photophysical characteristics. This paper investigates the optical and photophysical properties of malachite green as a laser dye in different solvents with different polarities.
2 Experimental
2.1 Materials
The chemicals that were utilized in this investigation were Malachite green (MG) and various spectroscopic grade solvents such as 1,4-Dioxane, DMF, Ethanol, Acetone and Methanol with purity of 95–99%. All chemicals were used without further purification.
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2.2 Sample preparation
Malachite green was dissolved in the different solvents with a concentration of 10–5 mol/l. Because they cover a wide range of polarity and exhibit good interaction with malachite green, acetone, dioxane, DMF ethanol, and methanol were selected as the solvents for the dye. The liquid samples were measured for their absorption and fluorescence spectra in a 1 × 1 cm quartz cell. And the quantum yield was measured for the samples in the different solvents relative to rhodamine B dye (as the standard).
2.3 Instrumentation
The absorption and excitation-emission spectra of malachite green diluted in various solvents can reveal some significant photo-physical characteristics. The measurement of absorption and excitation-emission spectra was done by a Biochrom Libra S50PC controlled scanning UV/Vis spectrophotometer, encompassing the wavelength range of 190–1100 nm, UV–Vis absorption spectra were acquired using 10 mm quartz cells and Shimadzu RF-1501 spectrofluorometer, respectively.
2.4 Computational investigations of malachite green
Utilizing the simulation techniques TD-DFT/CASTEP and TD-DFT/DMOl3, estimates of the gas phase frequency dimensions and molecular structure of MG were made. Using the TD-DFT/CASTEP and TD-DFT/DMOl3 software, the Perdew-Burke-Ernzerh (PBE) exchange, GGA functional correlations, pseudo-conserving norm, and DNP base set for the free molecules were determined (Becke 1992; Miehlich et al. 1989). The computations of the structural matrix simulation showed that 550 eV is the cut-off energy for plane waves. Using TD-DFT/DMol3 and TD-DFT/CASTEP frequency computation calculations at the gamma point, the optical, structural, and/or spectroscopic properties of MG were examined. The functional non-local interchange of Becke's law was demonstrated to be able to generate the functional B3LYP of MG in the gas phase (Frisch et al. 2009; Szpunar et al. 2022). The B3LYP technique for TD-DFT computations is based on WBX97XD/6-311G, as demonstrated in previous publications, and has produced outstanding results for structural spectrum correlation and experimental findings (Thabet et al. 2020). The Gaussian Potential Approximation System (GAP) addresses the general power and derivatives model in addition to the concurrent usage of multiple independent uncertainty models to allocate Gaussian and TD-DFT/CASTEP calculations for gas phase of MG models.
3 Results and discussions
3.1 TD-DFT simulations
Gaseous phase similarity properties of Malachite green were examined utilizing electrostatic potential and electron density. The DFT-DMOl3 computations' function of PWC was used to optimize the geometry for MG. The investigation of gaseous phase electron systems was done using electron density. However, by displaying the potential diagrams, any potential expansion of the MG gas phase was examined. The electron density and electrostatic potential studies provided support for the possibilities of electron transfer. MG was examined with respect to the physical–chemical properties of the gaseous phase using the electron density and electrostatic potential (Halium et al. 2022; kenawy et al. 2022). Using TD-DFT and TD-DFT/Gaussian thoughts, electron systems of the gaseous phase of MG can be computed based on the electron density Fig. 1a and b.
Fig. 1
a Electron density of malachite green gas phase, b electrostatic potential of malachite green gas phase by the applications of TD-DFT/DMOl3 programs
×
The energy gap was computed based on the difference between the molecular orbitals that are highest occupied (HOMO) and lowest unoccupied (LUMO), as illustrated in Fig. 2, and utilizing DFT-Dmol3 calculations. The simulations of the molecules' HOMO and LUMO states are directly responsible for the complex analysis of fragment molecular orbitals (FMOs). It can be deduced that the solvent utilized, which depends on the polarity, PH, and interaction between the dye and the solvent, affected the energy of HOMO and optical energy gab Eg.
Fig. 2
Absolute values of HOMO and LUMO states energy for malachite green in different solvents
×
Depending on the values of HOMO and LUMO states energies, it is easy to calculate important physio-chemical parameters like chemical potential (μ), softness (σ), global hardness (η), global softness (S), electronegativity (χ), global electrophilicity index (ω), and the maximum amount of electronic charge (ΔNmax) using the equations of (\(\mu =({E}_{HOMO}+{E}_{LUMO})/2),\) (\(\upeta ={(E}_{LUMO}-{E}_{HOMO})/2)\),\((\upchi =-\upmu )\),\((S=1/2\upeta )\), (\(\omega ={\mu }^{2}/2\upeta\)), (\(\upsigma =1/\upeta\)) and (\(\Delta {N}_{max}=-\mu /\eta )\) (Marahatta 2022). The values of EHOMO and ELUMO and the calculated parameters of (μ), (\(\upsigma )\), (S), (\(\upeta )\), (χ), (ω), and (\({\Delta N}_{max})\) are tabulated in Table 1. The stability of MG is indicated by the negative values of EHOMO and ELUMO, but the energy stability of the molecule upon receiving extra electronic charge is described by the critical quantum chemical characteristic (ω). (Ghazy et al. 2023a).
Table 1
Geometry constants for Malachite green as isolated molecules in different solvents
solvent
EHOMO
(eV)
ELUMO
(eV)
Egsim
(eV)
Egexp
(eV)
χ
(eV)
µ
(eV)
η
(eV)
S
(eV)
ω
(eV)
\(\Delta {{\text{N}}}_{{\text{max}}}\)
\(\sigma\)
no
− 3.975
− 3.382
0.593
–
3.678
− 3.678
0.296
1.686
22.850
12.425
3.378
Acetone
− 4.968
− 3.611
1.357
1.856
4.289
− 4.289
0.678
0.736
13.566
6.326
1.474
Dioxane
− 4.265
− 3.508
0.757
1.885
3.886
− 3.886
0.378
1.321
19.974
10.280
2.645
DMF
− 5.007
− 3.611
1.396
1.888
4.309
− 4.309
0.698
0.716
13.300
6.173
1.432
Ethanol
− 4.968
− 3.561
1.407
1.888
4.264
− 4.264
0.703
0.710
12.931
6.065
1.422
Methanol
− 5.002
− 3.611
1.391
1.909
4.306
− 4.306
0.695
0.719
13.339
6.195
1.438
3.2 Optical properties
Malachite green's absorbance spectra in various solvents are presented in Fig. 3a. It can be deduced that two absorbance bands, which emerged at 619 nm and 424 nm and are associated to n–π* and π–π* transitions, can be found there. Additionally, it can be deduced that altering the solvent had an impact on the location and intensity of the major absorption band. For the solvent combination of methanol, acetone, ethanol dioxane, and DMF, the absorbance band at 619 nm was redshifted. On the other hand, when the solvent was changed, the position of the absorption band at 424 was less impacted, with only a tiny red shift of 2 nm for the same solvent arrangement. The absorbance of MG in various solvents was studied using TD-DFT simulation Fig. 3b., and the results are very consistent with the actual data.
Fig. 3
a The absorption spectrum for malachite green in different solvents. b TD-DFT absorbance simulation
×
The difference in energy between the lowest unoccupied molecular orbit (LUMO) and the highest occupied molecular orbit (HUMO) is known as the energy gap, can be easily determined by using the well-known Tauc relation as(Ghazy et al. 2023c; Tauc et al. 1966):
where α is the absorption coefficient (\(\alpha =2.303A/x\)). At points where the values of the direct energy gabs take place, the extrapolated portion of the curve intersects the \(h\upsilon\) axis Fig. 4.
Fig. 4
Experimental calculations of bandgap energies for malachite green in different solvents
×
Due of the significant significance that the refractive indices play important role in optical applications, the refractive index real (n) and imaginary (k) components were determined for MG as (Khmissi et al. 2023; Rancourt 1996; Yu et al. 2003)
R is the film's reflectivity, which was determined using its transmittance T and absorbance A as (Henaish et al. 2019; King & Milosevic 2012) \(R=1-\sqrt{T.{e}^{A}}\), where k is the imaginary component of the index of refraction, sometimes referred to as the extinction coefficient. The electromagnetic photon's absorption or scattering within the material is also indicated by the extinction coefficient, K, which is calculated as \(k=\frac{\alpha \lambda }{4\pi }\). The refractive index and extinction coefficient of MG are shown in Fig. 5. As a function of wavelength for various solvents. It is possible to deduce that the refractive index value decreased from 1.47 when MG was dissolved in acetone to 1.20 when DMF was used as the solvent, with the solvents being changed in the following order: acetone, ethanol, methanol, dioxane, and DMF. The extinction coefficient likewise had the same behavior predicted.
Fig. 5
a refractive index b extinction coefficient dependence on wavelength for malachite green in different solvents
×
The real and imaginary components of the dielectric constant, ε1 and ε2, can be used to study the material's capacity to store electric energy as well as its ohmic resistance. In accordance with the values of the refractive index (n) and extinction coefficient (k), the real and imaginary parts of the dielectric constant Fig. 6. were computed as \({\varepsilon }_{1}={n}^{2}-{k}^{2}\) and \({\varepsilon }_{2}=2nk\), respectively(El-Nahass et al. 2004; Hill et al. 2000).
Fig. 6
Wavelength dependence of a real part b imaginary part of the dielectric constant for malachite green in different solvents
×
The real and imaginary components of optical conductivity σ1(ω) and σ2(ω) (respectively), are crucial in illustrating the material reaction to electromagnetic radiation. As shown in Fig. 7., σ1(ω) and σ2(ω) were estimated as \({\sigma }_{1}(\omega )={\varepsilon }_{o}{\varepsilon }_{2}\omega\) and \({\sigma }_{2}(\omega )={\varepsilon }_{o}{\varepsilon }_{1}\omega\), respectively(Ghazy et al. 2023b).
Fig. 7
Wavelength dependence of a real part b imaginary part of the optical conductivity for malachite green in different solvents
×
The observed fluorescence spectra of MG in various solvents are shown in Fig. 8. Using an excitation wavelength of 351 nm. When the solvent was switched between acetone, ethanol, dioxane, methanol, and DMF, the emission band that was determined to be blue shifted from 708 to 703 nm. On the other hand, it was discovered that the emission intensity dropped in that order: acetone, dioxane, DMF, methanol, and ethanol.
Fig. 8
Emission spectra for malachite green in different solvents
×
3.3 Photophysical properties
The effective number of electrons whose transition from the ground to the excited state provides the absorption region in the electronic spectrum is indicated by the oscillator strengths (f). (Calzaferri & Rytz 1995). The oscillator strength values were calculated from (Sakr et al. 2015):
where ε is the molar extinction coefficient and \(\nu\) is the wavenumber. The chemical structure determines the value of (f). The distance at which the original light intensity I0 decreased to (I = I0/e) where (e) is Euler's number (e ≅ 2.7), is known as the attenuation length Λ(λ) is given by (Elisei et al. 1997; Masetti et al. 1996):
where c is the molar concentration and ε(λ) is the molar extinction coefficient. The wavelength has a significant impact on the \(\Lambda\) values.
Utilizing the following formula, the transition dipole moment μ12 from the ground to the excited state was determined (Fei et al. 2023; Turki et al. 2006):
where Emax is the highest amount of energy absorbed in units of cm−1.
The Strickler–Berg equation can be used to theoretically predict a fluorophore's radiative decay rate constant (kr), also known as the fluorescence rate constant, which is based on the black body radiation law of Planck and the spontaneous emission rate of Einstein as given by (Kumar & Unnikrishnan 2001; Mukherjee et al. 2022):
In this case, n is the solid host's refractive index, F is the fluorescence intensity, \(\nu\) is the wavenumber, and ε (\(\nu\)) is the molar extinction coefficient at a specific wavenumber (\(\nu\)).
Then, using the following formula, the absorption and emission cross sections, \({\sigma }_{a}\) and \({\sigma }_{e}\) (\({cm}^{2}\)), respectively, are determined (El-Daly and Fayed 1999; Govindanunny and Sivaram 1980):
where c is the light's velocity, ε is the extinction coefficient, n is the solvent's refractive index, and λ is the emission wavelength, \(F\left(\lambda \right)\) is the normalized fluorescence spectrum since \(\int F\left(\lambda \right)d\lambda =1\) and \({\phi }_{f}\) is the fluorescence quantum yield. A excellent laser dye is one that has a larger value of \({\sigma }_{a}\) at the pumping wavelength.
Rhodamine-B (RB)/ CH3OH solution in quartz cuvette (1 \(\times\) 1 \(\times\) 4.5 \({{\text{cm}}}^{3}\)) with a quantum yield (ϕf) of 0.76 (Deshpande & Namdas 1996) was utilized as a reference to calculate the dye quantum yield of fluorescence. (ϕf). At different wavelengths, the emission spectra were adjusted for the monochromatic and photomultiplier responses. The solid with the dye embedded in it had its fluorescence intensity adjusted. The following relationship was used to calculate the quantum yield of a chemical in relation to a standard material (Ghazy et al. 2004; Kumar et al. 2001):
where A, I, and ϕ stand for the absorbance, the areas under the emission curves, and the fluorescence quantum yields, respectively.
Unknown and standard are indicated by the subscripts u and s, respectively. The refractive indices of the employed solvents are nu and ns. The calculation of fluorescence lifetimes (\({\uptau }_{{\text{f}}}\)) was done using:
$${\tau }_{f}={\tau }_{0}{\phi }_{f}$$
where (\({\tau }_{0}\)) is the natural lifetime (\({\tau }_{0}=\frac{1}{{k}_{r}}\)).
The quantum fluorescence yield \({\phi }_{f}\) is correlated with the intersystem crossing rate constant (Kisc) for (\({\phi }_{f}\)\(\approx\) 1) by the approximate relationship (Kubitz et al. 2023; Liao & Kelley 2012):
$${K}_{isc}=\frac{1-{\phi }_{f}}{{\tau }_{f}}$$
Using the relation, the energy yield of fluorescence (Ef) was determined as (Al‐shamiri et al., 2023; Bojinov and Grabchev 2004):
where \({\phi }_{f}\) is the fluorescence quantum yield, \({\lambda }_{A}\), \({\lambda }_{f}\) the wavelengths of maximum absorption and fluorescence, respectively.
The calculated photophysical properties of malachite green MG are listed in Tables 2 and 3. It may be deduced that the various dielectric properties of the solvent and the interaction between the dye and the solvent caused the photophysical characteristics of MG to change with altering the solvent. As a consequence, malachite green can be employed as a laser dye when dissolved in dioxane. The dissolution of MG in dioxane demonstrated the highest photophysical qualities because the quantum yield was found to be about 60% and the fluorescence lifetime was 1.21 ns.
Table 2
Absorbance properties of Malachite green in different solvents
Solvent
λabs (nm)
ε × 104 M-1cm−1
f
Λ cm
kr × 108s−1
σa × 10–16 cm2
μ12
(D)
Acetone (CH3COCH3)
620
6.78
0.67
0.64
1.32
2.61
17.49
1,4 Dioxane (C4H8O2)
624
1.79
0.22
2.42
0.49
0.68
10.05
DMF((CH3)2NOCH)
627
1.35
0.19
3.21
0.39
0.51
9.37
Ethanol (C2H5OH)
619
3.27
0.34
1.32
0.66
1.27
12.45
Methanol (CH3OH)
617
8.28
0.23
0.53
0.44
3.1
10.22
Table 3
Fluorescence properties of malachite green in different solvents media
Solvent
λf (nm)
ϕf
τf (ns)
σe × 10–16 cm2
Ef
kisc × 109
Acetone (CH3COCH3)
708
0.41
3.10
2.10
0.36
1.90
1,4 Dioxane (C4H8O2)
706
0.60
1.21
5.04
0.53
3.30
DMF((CH3)2NOCH)
709
0.25
6.25
2.09
0.22
1.2
Ethanol (C2H5OH)
714
0.21
3.19
1.54
0.18
2.47
Methanol (CH3OH)
707
0.30
6.81
1.14
0.26
1.03
4 Conclusion
As a laser dye, malachite green is investigated optically and photophysically. Malachite green was subjected to TD-DFT simulations in order to examine the electron density, electrostatic potential, and divergence between the HOMO and LUMO states in various solvents. Malachite green's optical characteristics were examined, and the results demonstrated how different solvents altered the material's optical characteristics by affecting the position and intensity of absorption. Malachite green's fluorescence spectra were also acquired, and based on the solvent utilized, they revealed one primary emission peak at 703–708. Optic property analysis revealed that when the solvent was changed from acetone to methanol, the energy gap increased from 1.856 to 1.909 eV. Additionally, it was shown that the range of maximum refractive index values for the various solvents was 1.47–1.20. On the other hand, it was discovered that the real dielectric constant for different solvents varied from 2.16 to 1.44. The solvent utilized also had an impact on photophysical properties. Malachite green's fluorescence quantum yield in various solvents was also examined. Having the shortest lifetime of 1.21 ns, the highest quantum yield and emission cross section values of 0.6 and 5.04 × 10–16 cm2, respectively, malachite green dissolved in dioxane was found to have the best optical and photophysical properties, suggesting that it might be employed as a laser dye.
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