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CHEMICAL PROBLEMS 2023 no. 4 (21) ISSN 2221-8688
UDC 536.42
LASER-INDUCED MODIFICATION ON SOME PROPERTIES OF PREPARED Cu(II)
COMPLEXES
Eman M. Ramadthan, Mahmoud A M Fakhri
Department of Medical Physics, College of Science, University of Mosul, Mosul, Iraq
Received 12.08.2023 Accepted 17.10.2023
Abstract: Two complexes - derived from dithiocarbamate ligand (L) and their adduct with nitrogen base of the general formula [Cu(L)2], [Cu(L)2(A)] obtained by the condensation of CuCl2.2H2O with L= diisopropyl amine dithiocarbamate and A=1,10-phenanthroline weve directly been synthesized and characterized by infrared spectra, metal content and magnetic measurement. Some properties of these two complexes, including UV/VIS absorption, melting point, and molar conductivity measurement are characterized in both cases before and after applying laser diode radiation with an emission wavelength of 532 nm. It found that laser has potential effects on Cu complexes under investigation for specific conditions and doses where new complexes have been observed, and spectral data and magnetic measurement showed a tetrahedral and octahedral geometries for [Cu(L)2] and[Cu(L)2(A)], respectively.
Keywords: Cu(II) complex; UV/VIS absorption; laser diode; melting point; magnetic measurement; molar
conductivity measurement
DOI: 10.32737/2221-8688-2023-4-370-3 78
1. Introduction
It is well-known that copper (Cu) is an extremely important element for all organisms. Cu and its related compounds are used for different vital fields of science and technology. In fact, Cu is a metal ion that is involved as a cofactor in several enzymes, in ROS (Reactive Oxygen Species) production, in the tumour progression promotion. Besides, Cu element is also detected at high levels in serum and tissues for several kinds of cancers in humans [1]. Cu complexes are used as catalysts for many biological and industrial processes. Also, the importance of the Cu complex currently lies in the fact that Cu may be used to cancer treatment [2]. Dithiocarbamate ligands coordinating through sulfur atoms with transition metals, dithiocarbamate complexes can present an extreme range of applications in chemistry, agriculture, medicine, and others [3,4]. The complexes with square planar shape of Ni(II)
and Cu(II) with potassium-based dithiocarbamate are directly prepared [5]. The neutral complexes are characterized by different measurement methods to ensure that the complexes are contained square planner geometry [5].
There is very limited research on the effect of lasers on Cu complexes [6]. However, laser type, operation mode, wavelength, output power, and other laser permeates should be considered in this field.
In the present work, the effects of a laser diode with an emission wavelength of 532 nm on UV/VIS absorption, melting point, magnetic measurement, and molar conductivity measurement of new Cu(II) dithiocarbamate complexes and their nitrogen bases have been considered for investigation, comparison before and after applying laser has been considered as standard criteria.
CHEMICAL PROBLEMS 2023 no. 4 (21)
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2. Experimental:
2.1. Materials and Methods
All starting materials were commercially obtained. The preparation was carried out under a nitrogen atmosphere. IR spectra were recorded on a Shimadzu FT-IR - ATR Bruker in the 4004000 cm-1 range by using KBr discs. On the other hand, electronic spectra were recorded on a Shimadzu UV 160 spectrophotometer by using dimethyl formaldehyde (DMF) for 10-3M solution of the complexes. Conductivity measurements were conducted on a 10-3 M solution of DMF at room temperature using a digital conductivity meter model - Eutech pc 700. Magnetic measurement was recorded by Bruker BM6 device under the temperature of 25 °C by using the method of Faraday. The metallic content was spectrophotometrically estimated by analytical Jena Model Nova AA-350. Melting points were specified on the electro thermal digital melting point apparatus.
2.2. Synthesis of dithiocarbamate ligand
An aqueous solution of sodium hydroxide
(0.4 g, 0.01 mole) was added with stirring to (1.7 ml, 0.01 mole) of isobutyl amine. The resulting mixture was cooled in ice, then (0.6
ml, 0.01 mole carbon sulphide was added drop wise with continuous stirring. The formed past was extracted by (100 cm3) ether filtered off, washed with ether, and dried in a vacuum [7].
2.3. Preparation of [Cu(L)2] complex
To a well-stirred solution of ligand (0.002
mole) in ethanol (15 cm3) was added (10 cm3) solution CuCh^O (0.17 gm, 0.001 mole) in ethanol solvent too. As a result, an immediate precipitation of the interested Cu complex is obtained. In addition, refluxing of focuses was also carried out in order of ensuring complete precipitation. It was also filtered off, then washed with ethanol, next with ether. Finally, it was dried under vacuum for several hours.
2.4. Preparation of [Cu(L)2 (A)] complex
A mixture of [Cu(Lh] (0.001 mole) in dimethyl formaldehyde (10 cm3) and 1,10 phenanthroline (0.001 mole ) in ethanol (10 cm3) was stirred for 3 hours, which afforded a thick precipitate, it was flittered then washed with ethanol and, as a final step, dried under a vacuum.
3. Procedure and laser parameters
Laser-induced modification on Cu (II) complexes in the liquid state were carried out by exposing these complexes to a semiconductor laser radiation in a different time (t) ranging from 0 to 45 minutes (m) with the interval of 15 m, it is clear that 0 m represents the reference (sample without radiated by laser). Laser parameters used in this investigation are listed in Table1. Laser power (P) is defined as:
P = E / t,
where E is laser energy. Laser beam diameter (d) on the samples is measured to be 1.25 cm. Since the laser beam is the circle, the spot area (A) on the interested samples is found to be: A = 1.23 cm2
Laser dose (D) can be calculated as [8]:
D = E / A
For times of 15, 30, and 45 m, doses were: 2.44, 4.87, and 7.3 J/cm2 respectively.
Table 1. Laser parameters used for the study.
Parameter Symbol Value Unit
Wavelength A 532 Nm
Operation mode CW
Output power P 200 Mw
Irradiation area (spot A 1.23 cm2
size)
Power density I 162.6 mW/
(Irradiance) cm2
4. Results and discussion
The chemical and physical parameters and conditions for obtaining of various d-elements with nitrogen and sulphur-containing ligands were analyzed [4,9]. Laser-induced modification on absorption, melting point, molar conductivity measurement of Cu(II) complexes were examined through considering the effect of the used laser irradiation on these properties for Cu(II) complexes (the samples are in liquid phases) by measuring these quantities before and after the exposure to laser radiation with different doses.
First of all, the suggested geometrical structures of the prepared complexes are shown in Fig. 1. Bi dentate coordination of ligand, the physical properties of ligand, and complexes
are shown in Table 2, melting points at (315, 208)°C for complex 1 and complex 2 without laser and (160-295)°C for complex 1 and complex 2 with laser.
The low values of molar conductivity under investigation complexes indicate that all prepared complexes are not electrolytes in DMF, [9,10]. Table 2 shows this property before and after applying the used laser.
The measurements of the magnetic moment of the complexes in Table 2, were measured at 25 °C. The magnetic moment for Cu (II) (1,2) is (2.26, 1.69 ) B.M. respectively suggests a tetrahedral and octahedral configuration [11,12].
[CU (CyHi4NS2)2]
[Cu (CyHi4NS2)2(Cl2H8N2)]
Fig. 1. Suggested structures of the prepared complexes.
UV/Vis spectra of the ligand with their two complexes in 10-3M DMF solution were recorded; they are listed in Table 3. The electronic spectra of the complex (1) show one band at 674 nm, this band is assigned to a 2T2^2E transition that suggests a tetrahedral geometry around copper ion [13] as indicated in
Fig. 2(a). Fig. 2(a) shows the standard absorption spectrum of complex 1(i.e. without applying laser irradiation); while Fig. 2(b) shows the standard absorption spectrum of the complex 2. It is clear that both of them were subjected and applied for a wide range of spectrum spanning from the visible to near-
infrared (IF) of the electromagnetic spectrum. The normal and well-known peaks for these complexes can be clearly shown. Some regions
of spectra ranges will be considered for the present work
Table 2. Physical properties of t
he com
jlex before and after applying laser diode radiation.
No. Compound Colour Л 10-3M DMF Л10-3 M DMF With laser ^eff. (B.M) MP. (C)° M.P.(C)° With laser MX Cal (found)
1 [ Cu (C7H14NS2)2] Brown 24.3 15m. 15 2.26 315 15m. 247 15.28 (14.92)
30m. 29 30m. 160
45m. 36 45m. 295
2 [ Cu (C7H14NS2MC12H8N2) ] Green 45 15m. 27 1.69 208 15m. 159 10.66 (9.89)
30m. 35 30m. 189
45m. 14 45m. 201
Table 3. Electronic and IR spectral data ligand and complexes before and after applying laser
diode radiation.
Comp .No. U.V. -Vis bands nm U.V. -Vis bands nm With laser IR bands cm-1
V (C-S) V (C=S) V (M- S) V (M-N) V (C-N) V (C-H)
C7HmNS2 314,301 848 1064 - 1470 3120
1 674 433—264 754 1028 482 - 1456 3101
2 992,608, 380 261—385 850 1036 467 418 1458 3064
Cu (II) Complex (2) shows three absorption bands at 992 nm, 608nm, 380 nm, which are belonged to three transitions of
2B1g^2Ä1g, 2B1g^2B2g, and 2B^2Eg in an octahedral configuration [6,14] as shown in Fig. 2(b).
MX>0 1000 0 1100.0
Fig. 2(a). Spectrum electronic of [Cu (C7H14NS2)2] without applying laser.
Fig. 2(b). Spectrum electronic of [Cu (C7H14NS2)2(C12H8N2)] without applying laser.
Used laser was applied on complex 1 for times of 0, 15, 30, and 45 minute. New bands at the wavelength ranging from 433 nm to 264 nm appeared. These interesting results can be attributed to the transitions of n^ n and n ^ n*. The disappearance of the wideband from 642 nm suggests that the shape was tetrahedral as indicated in Fig. 3(a). This result may suggest that the complex was decomposed under laser irradiation exposure. For complex 2 the same above parameters were used but new bands at the wavelength ranging from 261 nm to 385nm were observed instead. The interesting results
can also be attributed to the transitions of n^ n*and n ^ n*. The disappearance of the wideband from (992 nm and 608nm) suggests that the shape was octahedral geometry as indicated in Fig. 3(b). This result may suggest that the complex was also decomposed by the applied laser.
One can observe that the effects of laser irradiation with a wavelength of 532 nm on the Cu complexes were non-linear. This result may be interpreted for appearing new complexes as it can be seen on the UV/VIS spectra in Fig. 3 (a, b).
15 ill /
45 m 3(im
Fig. 3(a). Spectrum electronic of [ Cu (C7H14NS2)2] with applying laser.
30 ni
1V / \ in
15 I
u m « ■
Fig. 3(b). Spectrum electronic of [Cu (C7H14NS2)2(C12H8N2)] with applying laser.
Fig. 4(a). The IR Spectrum of complex [Cu ^7^4^2)2]
Fig. 4(b). The IR spectrum of co
Table 3 shows the most influenced bands which are recorded by IR spectra for complexes examined. In IR spectrum of the ligand the sharp bands observed at 1064 cm-1, and 848 cm-
3lex[Cu (C7H14NS2MC12HN2)].
1 which belong to the v ( C=S) [6,15], and v (C-S) [16,17]. The infrared spectra of the complex (1) showed a sharp band at the 482, 1028,754 cm-1 which assigned to v (M-S), v ( C=S), v (C-
S) [18,19] respectively, see Fig. 4(a) ,while for (M-S), v ( M- N), v (C=S), v (C-S) [20,21] complex (2) the following bands are observed at respectively. See Fig. 4(b). 467, 418, 1036, 850 cm-1 which assigned to v
5. Conclusion
The green laser emission with a wavelength of 532 nm has potential effects on the properties of Cu (II) with diisopropylamine dithiocarbamate and Cu(II) and 1,10-phenanthroline. In this way, new Cu complexes
can be synthesized and characterized before and after applying laser. Besides, other laser types and wavelengths with different doses may be considered for preparing new complexes.
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ЛАЗЕРНО-ИНДУЦИРОВАННАЯ МОДИФИКАЦИЯ НЕКОТОРЫХ СВОЙСТВ
ПОЛУЧЕННЫХ КОМПЛЕКСОВ Си(11)
Эман М. Рамадтан, Махмуд А.М. Фахри
Кафедра медицинской физики, Университет Мосула, Ирак
Аннотация: Два комплекса - производные дитиокарбаматного лиганда (Ь) и их аддукта с азотистым основанием общей формулы [Си(Ь)2], [Си(Ь)2(А)], полученные конденсацией СиС122Н20 с Ь = дитиокарбаматом диизопропиламина и А=1,10-фенантролином были непосредственно синтезированы и охарактеризованы с помощью инфракрасных спектров, содержания металлов и магнитных измерений. Некоторые свойства этих двух комплексов, включая поглощение УФ/ВИД, температуру плавления и измерение молярной проводимости, охарактеризованы в обоих случаях до и после применения излучения лазерного диода с длиной волны излучения 532 нм. Было обнаружено, что лазер оказывает потенциальное воздействие на исследуемые комплексы Си при определенных условиях и дозах, при которых наблюдались новые комплексы, а спектральные данные и магнитные измерения показали тетраэдрическую и октаэдрическую геометрию для [Си(Ь)2] и [Си(Ь) 2(А)] соответственно.
Ключевые слова: комплекс Си(П); поглощение УФ/ВИД; лазерный диод; температура плавления; магнитные измерения; измерение молярной проводимости
SiNTEZ EDiLMiS Cu(II) KOMPLEKSiNiN B9Zi XASSOLORlNiN LAZER- iNDUKSiYA
MODiFiKASiYASI
Eman M. Ramadtan, Mahmud A.M. Faxri
Tibbi fizika kafedrasi, Mosul Universiteti, Iraq
Xülasa: [Cu(L)2], [Cu(L)2(A)] ümumi düsturuna malik iki kompleks - ditiokarbamat liqandinin (L) töramalari va onlarin CuCl22H2O ila kondensasiyasi ila alda edilan azot asasli alavasidir. Burada L = diizopropilamin ditiokarbamat va A =1,10-fenantrolin birba§a olaraq sintez edilmi§ va, metal tarkibi, maqnit öl9malari va infraqirmizi spektrlardan istifada etmakla tadqiq edilmi§dir. Bu iki kompleksin bir sira xüsusiyyatlari, o cümladan UV/Vis udma, arima nöqtasi va molyar ke?iricilik öl9malari, har iki halda 532 nm lazer diod §üalanmasinin tatbiqindan avval va sonra xarakteriza edilmi§dir. Lazerin müayyan §artlarda va dozalarda tadqiq edilmi§ Cu komplekslarina potensial tasir göstardiyi müayyanla9dirilmi§, bu zaman yeni komplekslar mü§ahida edilmi§ va spektral malumatlar va maqnit öl9malari müvafiq olaraq [Cu(L)2] va [Cu(L)2(A)] ü9ün tetraedrik va romboedrik qurulu§ nümayi§ etdirmi§lar.
A?ar söztar: Cu(II) kompleksi; UV/VIS udma; lazer diodu; arima temperaturu; maqnit öl9malari; molyar ke9iriciliyin öl9ülmasi
