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The synthesis and characterization of s-Triazine polymer complexes containing epoxy groups
Journal Pre-proof The synthesis and characterization of s-Triazine polymer complexes containing epoxy groups Neslihan Orhan, Saban Uysal PII:
S0022-2860(19)31479-6
DOI:
https://doi.org/10.1016/j.molstruc.2019.127370
Reference:
MOLSTR 127370
To appear in:
Journal of Molecular Structure
Received Date: 16 September 2019 Revised Date:
3 November 2019
Accepted Date: 5 November 2019
Please cite this article as: N. Orhan, S. Uysal, The synthesis and characterization of s-Triazine polymer complexes containing epoxy groups, Journal of Molecular Structure (2019), doi: https://doi.org/10.1016/ j.molstruc.2019.127370. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
The Synthesis and Characterization of s-Triazine Polymer Complexes Containing Epoxy Groups Neslihan ORHAN1 and Saban UYSAL2* 1
University of Karabuk, Institue of Natural and Applied Sciences, Department of Polymer
Engineering, 78050 KARABUK- TURKEY 2
University of Karabuk, Faculty of Science, Department of Chemistry, 78050 KARABUK-
TURKEY *Corresponding Author: ph: +9 (0532) 303 30 35 e-mail: [email protected]
It has been synthesized in this study that s-triazine based monomeric complexes including epoxy groups and their polymeric structures. For this reason, cyanuric chloride (I) has been used as starting material. 5-(4,6-dicholoro-2-1,3,5-triazine-2-ylamino)isophtalic acid coded as “III” has been obtained from the reaction of 5-aminoisophtalic acid II and I at -5 ºC with sodium bicarbonate in aqua/acetone media. Bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5triazine-2-ylamino)izophtalate coded as “V” was synthesized from the reaction of epichlorohydrin (IV) and III in aqua/acetone media with KOH at +2 ºC. In aqua/ethanol media at 60 ºC, monomeric metal complexes (VI, VII and VIII) were obtained from the reaction of V and/or Mn+2, Co+2 and Ni+2. s-Triazine based polymeric metal complexes (IX-XIV) were obtained from the reaction of the monomeric metal complexes and 3,4dihydroxybenzaldehyde/o-phenylenediamine in 1,4-diaxane media with DIPEA at 60 ºC. The structure of ligands, monomers and polymers were characterized using 1H-NMR and 13
C-NMR, FTIR, ESI-MS, UV-vis spectrophotometers, TGA and elemental analyses.
Metal contents in the prepared monomeric and polymeric complexes were determined by inductively coupled plasma atomic emission spectrophotometer (ICP-AES). Magnetic behaviors of the synthesized novel monomeric and polymeric complexes were also investigated. And, these compounds were determined to be high-spin distorted octahedral Mn(II), distorted octahedral Co(II) and distorted octahedral Ni(II).
Keywords: epoxy, oxirane, complex, epichlorohydrin, s-triazine, polymer.
1
1.
Introduction s-Triazine compounds are used as the ligand in coordination chemistry. They also act
as various chelating agents for the synthesis of metal complexes having interesting molecular and supramolecular structures [1-3]. s-Triazine polymers are also used for metal ion extraction [4, 5]. 1,3,5-Triazine-containing ligands are stable molecules even at above the temperature of 150 °C. They only undergo hydrolysis in the presence of concentrated mineral acids via thermal treatments [6]. In recent years, researchers have focused the synthesis of linear magnetic polymers based on s-triazine compounds due to their importance in industrial applications [7] and their potential applications in data storage and quantum computing devices [8-13]. Also, these s-triazine derivatives are important heterocyclic compounds for potential applications in pharmaceutical and biological treatments [14-21]. s-Triazine compounds are also used in various industries including plastic [22], paper [23, 24], electrical [25, 26], textile [27, 28], dye [23, 24], purification [29-33] and telecommunication system [34-38]. Moreover, these compounds have been widely used for the fabrication of light detecting optical switches and image recorders [39-43], production of flame retardant materials with low toxicity [44, 45] and an alternative to some petrochemical raw materials [46-57].
In previous works, dendrimer s-triazine complexes [58,59], linear [M(salen/salophen)] capped s-triazine-based polymeric complexes [60,61] have also been studied. Via their oxygen atoms, epoxy groups can be bonded to the metal atoms. It is seen in the literature that the oxirane group was coordinated from the axial position(s) to the central atoms of the chelates which are in the square planar and square pyramidal forms. [62]. In another previous work, linear [M(salen/salophen)] capped s-triazine-based polymeric complexes containing epoxy and dopamine groups have also been studied (Figure 1) [63]. In the present work, epoxy containing s-triazine polymer complexes were synthesized using cyanuric chloride as starting material. The s-triazine derivatives are usually synthesized using cyanuric chloride owing to the practical exchange of chlorine atoms with temperature. Substituted s-triazine derivative was produced by reaction between 5aminoisophtalic acid and 2,4,6-trichloro-1,3,5-triazine, where the chloride was substituted by the amine group. The acidic -OH groups of the product were treated with epichlorohydrin, and monomer ligand that contains two epoxy groups were obtained. This
2
ligand was reacted with MX2.4H2O (M= Mn(II), Co(II) and Ni(II); X = Cl- and CH3COO-) to form monomer complexes which were polymerized with 1,2-phenylenediamine and 3,4dihydroxybenzaldehyde such that polymeric complexes were obtained. The thermal behaviors of these polymers were investigated in the temperature range of 50-900 °C. Then, the magnetic susceptibility values of these polymers were measured. Finally, Uv-Vis spectra of some of them were taken in range of 200-800 nm.
2.
Experimental
2.1. Reagents and solvents Together with epichlorohydrin and all the solvents, cyanuric chloride (1), 5aminoisophtalic acid, 3,4-dihydroxybenzaldehyde and o-phenylenediamine were bought from Sigma and they were used without further purification. The 1H NMR and
13
C NMR
spectra of the compounds were taken with an Agilent NMR VNMRS spectrometer at 400 MHz and 100 MHz, respectively, through their dimethylsulfoxide (DMSO-d6) solutions. The internal standard of the NMR measurements was tetramethylsilane (TMS). IR spectra were measured by a Thermo SCIENTIFIC NICOLET IS5 FT-IR spectrometer using the ID5 ATR Polarization Accessory (4000–440 cm−1). Thermogravimetric Analysis (TGA) were performed using Hitachi STA7300 Thermal Analysis System. Elemental analyses were performed on a Leco 932 CHNS instrument where the results were in good agreement with the theoretical values. The metal contents of each complex were determined on a Varian, Vista AX CCD Simultaneous model Inductively coupled plasma atomic emission spectrophotometer (ICP-AES). Using ethyl alcohol and chloroform as solvents, the mass spectra were measured in a Thermo TSQ Quantum Access Max LCMS/MS spectrometer. Melting points were determined using an Electro Thermal IA9000 system, while the pH values were obtained from a Milwaukee Mi 150 pH meter. Magnetic moment values of the metal complexes were determined with a Sherwood Scientific MX Gouy magnetic susceptibility apparatus using the Gouy method with Hg[Co(SCN)4] as calibrant. The effective magnetic moments per metal atom, µeff, were calculated using the well-known formula µ eff = 2.84(XMT)1/2 B.M., where XM is the molar susceptibility.
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2.2. Synthesis of 5-(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalic acid (III)
A solution of natrium bicarbonate (NaHCO3) (0.84 g, 10.00 mmol) in 20 mL water was added to a solution of cyanuric chloride (1.84 g 10,00 mmol) in 20 mL acetone for 15 minutes as stirring continuously at -5 ºC. After 30 minutes, 5-aminoisophtalic acid (1,81 g, 10,00 mmol) in 20 mL acetone, which is stirring for 10 minutes at room temperature, was added to the first solution for 30 minutes as stirring continuously. And, then it was stirred for 2 hrs. at -5 ºC. A solution of natrium bicarbonate (NaHCO3) (0.84 g, 10.00 mmol) in 20 mL water was added to this mixture and stirred for 3 hrs. at -5 ºC. Its pH was set to 7.00 with adding 1 M HCl dropwise. This mixture was kept at 4 ºC for 12 hrs. and filtered under vacuum. The solid white product was also filtered and washed with diethyl ether, and then it was put into a vacuum cabinet for drying. Finally, the products were purified using column chromatography (ethylacetate/n-hexane - 1/3 v/v) (Scheme 1). The characteristic FT-IR bands (cm−1) of (III); (C=Ntrz) 1625; (C-Har) 3125, 3150; (C=O) 1666; (C-Car) 1451, 1568; (N-H) 3391str, 1510bend; (COO) 1371; (OH) 3287 2.3.
Synthesis of bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izoph talate (V)
5-(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalic acid (0,99 g, 3,00 mmol) was solved in 20 mL acetone, and cooled to 2 °C. KOH (0,34 g, 6,00 mmol) in 20 mL aqua was added to the solution. After 30 minutes, epichlorohydrin (0,52 mL, 6,00 mmol) in 20 mL acetone was added drop by drop to the first solution stirring at 2 °C for 15 minutes. The solution was stirred for 3 hours at the same temperature. Finally, the pH of the system was adjusted to around 7.00 with 1.00 M HCl. The mixture was allowed to mature in cooler for 12 hours. The yellow solid formed was washed with 10 ml of diethylether, filtered quickly and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of (V); (C=Ntrz) 1622; (C-Har) 3285(broad); (CHaliph) 2910, 2970, 2805; (C=O) 1667; (C-Car) 1564, 1482; (N-H) 3370str, 1510bend; (COO) 1362; (Oxirane) 1275, 900
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2.4. Synthesis of monomeric M(II) complexes (M = Mn2+, Co2+ and Ni2+) of bis(oxiran-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate (VI, VII and VIII)
1 mmol of MnCl2.4H2O/Co(CH3COO)2.4H2O/NiCl2.6H2O in 10 mL aqua were added to bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate (V) (0,44g, 1,00 mmol) in 10 mL ethanol at 60 ºC. The solution was stirred for 3 hours at the same temperature. After 2 hrs., the pH of the system was adjusted to around 5.50 with 1.00 M KOH. The solution was stirred for 3 hours at 60 ºC. The mixtures were allowed to mature at room temp. for 12 hours. Light brown, light purple and light green colored precipitates, respectively are rapidly filtered, washed with 10 mL of diethylether and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of monomeric complexes (VI–VIII); (VI): (C=Ntrz) 1622; (C-Har) 3131(broad); (C-Haliph) 2831, 2903; (C=O) 1738; (C-Car) 1557; (N-H) 1278str, 1510bend; (COO) 1364; (Oxirane) 1296, 900 - (VII): (C=Ntrz) 1622; (C-Harom) 3272(broad); (C-Haliph) 3272(broad); (C=O) 1734; (C-Car) 1557; (N-H) 3272str (broad), 1511bend; (COO) 1359; (Oxirane) 1319, 897 - (VIII): (C=Ntrz) 1621; (C-Harom) 3278(broad); (C-Haliph) 2903, 2838; (C=O) 1734; (C-Car) 1557; (N-H) 3278str (broad), 1514bend; (COO) 1362; (Oxirane) 1320, 899 2.5. Synthesis of polymeric M(II) complexes (M = Mn2+, Co2+ and Ni2+) of bis(oxiran-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate
VI/VII/VII (1,00 mmol, 0,57/0,62/0,57 g) were solved in 20 mL 1,4-dioxan at 60 ºC. 3,4-dihydroxybenzaldehyde/o-phenylenediamine (0,14/0,11 g, 1,00/1,00 mmol) in 20 mL 1,4-dioxan were added to the first solutions stirring at 60 ºC. Then, N,Ndiisopropylethylamine (0,17 mL, 1,00mmol) were added to these mixture. The reactions were terminated after 48 hours. These products were allowed to mature at room temperature, washed with 10 mL diethylether and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of polymeric complexes (IX–XIV); (IX): (C=Ntrz) 1621; (C-Harom) 3138; (C-Haliph) 2980, 2950, 2880, 2827; (C=O) 1745, 1660; (C-Car) 1557, 1563; (N-H) 3277str,1512bend; (COO) 1361; (C-OPhen) 1260; (Oxirane) 1293, 900- (X): (C=Ntrz) 1622; (C-Harom) 3120(broad); (C-Haliph) 2807, 2882; (C=O) 1745;
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(C-Car) 1557, 1563; (N-H) 3271str, 1510bend; (COO) 1360; (Oxirane) 1261, 900 - (XI): (C=Ntrz) 1622; (C-Harom) 3119(broad); (C-Haliph) 2950, 2884, 2825; (C=O) 1662, 1745; (CCar) 1557, 1563; (N-H) 3285str,1513bend; (COO) 1361; (C-OPhen) 1294; (Oxirane) 1262, 899 - (XII): (C=Ntrz) 1622; (C-Harom) 3138(broad); (C-Haliph) 2825, 2882 (C=O) 1745; (CCar) 1563; (N-H) 3275str
(broad),
1511bend; (COO) 1361; (Oxirane) 1261, 900 - (XIII):
(C=Ntrz) 1621; (C-Harom) 3119(broad); (C-Haliph) 2825, 2882; (C=O) 1741, 1682; (CCar)1556, 1563; (N-H) 3275str
(broad),
1514bend; (COO) 1361; (C-OPhen) 1292; (Oxirane)
1256, 899 - (XIV): (C=Ntrz) 1622; (C-Harom) 3138(broad); (C-Haliph) 2812, 2882; (C=O) 1663; (C-Car) 1512, 1558; (N-H) 3275str
(broad),
1514bend; (COO) 1365; (Oxirane) 1260,
900.
3. RESULTS AND DISCUSSIONS In this study, 2,4,6-trichloro-1,3,5-triazine was used as the starting material. In the presence of sodium bicarbonate in acetone medium, 5-(4,6-dichloro-1,3,5-triazine-2ylamino)isophthalic acid (III) was obtained from the reaction of cyanuric chloride with 5aminoisophthalic acid at -5 ° C. Fujiwara test was performed to confirm that the reaction was unidirectional and the result was evaluated as positive [64]. In the presence of KOH in acetone/water
medium,
bis(oxiran-2-ylmethyl)5-(4,6-dichloro-1,3,5-triazine-2-
ylamino)iso-phtalate (V) was obtained from the reaction of an equivalent III and two equivalent epichlorohydrin (as using 10% excess of epichlorohydrin) at +2 ° C. These monomer ligands (III and V) were identified using 1H-NMR,
13
C-NMR, FTIR, FT-IR
elemental analysis and ESI-MS analyzes. Monomeric metal (Mn2+, Co2+ and Ni2+) complexes (VI, VII and VIII) were obtained from the reaction of bis(oxiran-2-ylmethyl)5(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalate
with
MnCl2.4H2O,
Co(CH3COO)2.4H2O and/or NiCl2.6H2O in ethanol media at 60 °C. Polymeric s-triazine complexes (IX-XIV) including epoxy groups were obtained from the reaction of the monomeric complexes with 3.4-dihydroxybenzaldehyde and/or o-phenylenediamine in the presence of DIPEA in 1,4-dioxan media at 60 °C. The structures of these monomeric and polymeric complexes were also identified using FTIR, elemental analysis, ESI-MS, TGA and magnetic susceptibility analysis (Table 1). The polymerization degree of the polymers was determined by the molecular weight determination study with the viscometer.
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Scheme 1: The synthetic route of ligand, monomeric and polymeric complexes.
3.1. Interpretation of 1H-NMR and 13C-NMR Spectra of Ligands When investigated 1H NMR spectra of III and V obtained as target ligands, for III a singlet was observed at δ=6.970 (2Ha) ppm for seconder -NH2+- group linked to s-triazine ring owing to proton migration from the acid group to the amine group, a singlet was observed at δ=8.166 (2Hb) ppm, a singlet was observed at δ=8.364 (2Hc) ppm for aromatic C-H group, and four singlets were observed between δ=10.588-11.344 (Hd and He) ppm for acidic OH groups. The reason why acidic hydrogens are observed in the spectrum is due to the fact that these hydrogens can see different environments and at the same time they are remote bond interactions (Figure 2A).
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Table 1: The elemental analysis data and physical properties of all ligands and complexes. [Emprical Formula] (Compound Codes) [C11H6N4O4Cl2] (III) [C17H14N4O6Cl2] (V) [C17H14N4O6Cl4Mn] (VI) [C21H20N4O10Cl2Co] (VII) [C17H14N4O6Cl4Ni] (VIII) [C24H18N4O9Cl2Mn]n (IX) [C23H20N6O6Cl2Mn]n (X) [C28H24N4O13Co]n (XI) [C27H26N6O10Co]n (XII) [C24H18N4O9Cl2Ni]n (XIII) [C23H20N6O6Cl2Ni]n (XIV)
µeff (B.M.) 296 K Dia Dia 5.84 3.82 2.79 5.76 5.78 3.77 3.79 2.75 2.76
M.P °C Color
[Mw] Yield %
197* White 265* Yellow 365* Light Brown 415* Light Purple 400* Light Green 395* Dark Green 380* Brown 430* Dark Purple 425* Dark Purple 385* Light Brown 405* Green
[327.98] 84 [440.03] 65 [566.90] 62 [616.99] 65 [569.90] 67 [632.27] 58 [602.29]n 55 [683.44]n 52 [653.46]n 57 [636.02]n 59 [606.04]n 60
C 40.15 40.12 46.284 6.15 36.01 35.94 40.80 40.74 35.77 35.73 45.59 45.54 45.87 45.83 49.21 49.15 49.63 49.54 45.32 45.25 45.58 45.49
Contents (%) Calculated/Found H N 1.84 17.02 1.83 16.96 3.20 12.70 3.18 12.66 2.49 9.88 2.47 9.85 3.26 9.06 3.23 9.05 2.47 9.82 2.45 9.81 2.87 8.86 2.84 8.84 3.35 13.95 3.31 13.90 3.54 8.20 3.51 8.16 4.01 12.86 3.98 12.77 2.85 8.81 2.84 8.80 3.33 13.87 3.30 13.80
M** 9.69 9.66 9.53 9.50 10.28 10.25 8.69 8.65 9.12 9.10 8.62 8.60 9.02 9.00 9.23 9.21 9.68 9.65
Bold elemental analysis values are found values, M.P = Melting point, *Decomposition Point, **M = Mn(II), Co(II) and Ni(II), µeff = Effective Magnetic Moment.
After the deuterium exchange, disappearing the peaks for acidic group between δ=10.588-11.344 ppm, and at δ=6.970 ppm observed as broad slightly for NH2+ group, and observing a singlet at δ=6.002 (1H) ppm for seconder NH group are a good evidence of formation of the ligand III (Figure 2B). Similarly, disappearing the peaks for acidic group between δ=10.588-11.344 ppm, and observing a dublet at δ=4.421 (4Hd) ppm for the next to oxirane groups, a multiplet at δ=3.138 (2He) ppm for oxirane groups, a dublet at δ=2.285 (4Hf) ppm for oxirane groups are evidence that the original target ligand (V) was obtained (Figure 3) [58, 59, 63, 65]. When the
13
C NMR spectra are examined for (III) and (V), carbon peaks of (III) are
encountered at δ=166.679 ppm for C1, δ=166.262 ppm for C2, δ=154.730 ppm for C7, δ=150.375 ppm for C3, δ=138.290 ppm for C5, δ=132.335 ppm for C4, δ=126.038 ppm for C6, and carbon peaks of (V) are encountered at δ=166.679 ppm for C1, δ=166.262 ppm for C2, δ=154.730 ppm for C7, δ=150.375 ppm for C3, δ=138.290 ppm for C5, δ=132.335 ppm
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for C4, δ=126.038 ppm for C6, δ=66.481 ppm for C8, δ=49.662 ppm for C9, δ=44.445 ppm for C10. These recorded 13C and 1H resonances are consistent with the literature [58, 59, 63, 65] (Figure 4 and Figure 5).
3.2. Interpretation of FTIR Spectra of Ligand and All Complexes The characteristic FTIR bands for both ligands and all monomeric and polymeric complexes are given in experimental section. The bands at 1666 and 1667 cm-1, 3391 cm-1 and 1510 cm-1 for carbonyl, N-H stretching and N-H bending of ligand III, respectively, have verified that 5-aminoisophtalic acid has attached to s-triazine ring with its N atom. Similarly, which the bands at 1575 cm-1 and 900 cm-1 for oxirane ring stretching and oxirane ring bending of ligand V, respectively, are observed and which the band at 3287 cm-1 for OH groups are disappeared have also verified that epichlorohydrin has attached to carboxylate groups of ligands III. In addition, the observation of the band at 1371 cm-1 for COO bending of ligand III at a lower frequency of ~9 cm-1 for the ligand V also proved that the epichlorohydrin group is attached to the carboxylate groups [58-61, 63, 65-74] (Figure S1, provided as Supporting Information). When examining the FT-IR spectra of the monomer complexes, different from the FTIR spectrum of ligand V, the bands for the carbonyl groups in all the complexes were approximately 71-67 cm-1 at a higher frequency, and the bands for epoxy ring stretching vibrations in all the complexes were approximately 21-44 cm-1 at a higher frequency were observed. These data prove that the ligand V is coordinated to the metal ions (Mn2+, Co2+ and Ni2+) with the carbonyl oxygens and the oxirane oxygens [62, 63] (Figure S1, provided as Supporting Information). Similarly, evaluating the FT-IR spectra of the polymer complexes, characteristic bands of the polymerizing groups unlike the monomer complexes have been observed (Figure S2 and Figure S3, provided as Supporting Information). These bands at 1260 cm-1, 1294 cm-1 and 1291 cm-1 are observed for phenolic stretching vibration of IX, XII and XIII, respectively, and these bands at 1660 cm-1, 1662 cm-1 and 1682 cm-1 are also observed for carbonyl groups of aldehydes, respectively.
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3.3. Interpretation of TGA Curve of Some of The Complexes Thermal analysis of the ligands, monomeric and polymeric complexes were performed where 1.00 mg sample was heated in a nitrogen atmosphere at the rate of temperature rise 10 °C/min in the range of 50-900 ºC. The weight losses of all complexes determined from the TGA analyses are in good harmony with the calculated values (Table 2). Table 2. Decomposition steps with the temperature range, weight loss and estimated decomposed groups for ligands and all complexes. Compounds [C11H6N4O4Cl2] (III) [C17H14N4O6Cl2] (V) [C17H14N4O6Cl4Mn] (VI) [C21H20N4O10Cl2Co] (VII) [C17H14N4O6Cl4Ni] (VIII) [C24H18N4O9Cl2Mn]n (IX) [C23H20N6O6Cl2Mn]n (X) [C28H24N4O13Co]n (XI) [C27H26N6O10Co]n (XII) [C24H18N4O9Cl2Ni]n (XIII) [C23H20N6O6Cl2Ni]n (XIV)
Step
Temp. range (ºC)
W. Loss (%) Found (Calcd.)
Estimated decomposed group(s) corresponding to weight losses
1 2 1 2 3 1 2 3 1 2 1 2 3 1 2 1 2 1 2 1 2 1 2 1 2
80-320 320-900 80-365 365-445 445-900 95-385 385-481 481-900 73-425 425-900 90-467 467-612 612-827 200-580 580-900 200-580 580-900 200-450 450-815 200-445 445-820 300-500 500-900 300-500 500-900
27.36 (25.53) 46.60 (74.47)* 25.88 (23.12) 19.95 (12.28) 13.70 (64.60)* 14.78 (20.13) 16.22 (15.52) 25.00 (38.08)* 33.63 (37.56) 44.08 (37,65) 40.04 (35.41) 15.14 (13.15) 14.45 (12.44) 31.50 (31.95) 14.00 (44.50)* 31.00 (33.54) 14.15 (41.73)* 30.02 (33.98) 20.03 (23.87) 30.00 (35.54) 22.00 (24.96) 34.80 (31.76) 44.04 (44.23) 35.04 (33.33) 44.02 (41.48)
-carbonate groups -the other organic groups -methyloxiran groups -carbonate groups -the other organic groups -methyloxiran groups -carbonate groups -the other organic groups -methyloxiran and carbonate groups -the other organic groups -methyloxiran and carbonate groups -benzene in the remaining structure -chlorine atoms -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network
*Decomposition of the compounds could not be completed because heating operation was terminated at 900 °C.
As for TGA curve of ligand, monomeric and polymeric complexes, TGA curve of all compounds have been given in Figure 6 and Figure 7. Weight losses for all complexes, decomposition temperature ranges and estimated decomposed group(s) corresponding to the weight losses have been given in Table 2, particularly. Decomposition of some compounds could not be completed because heating operation was terminated at 900 °C. It
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is believed that metal salts and s-triazine rings remain at 900 ° C without degradation (Figure 6 and Figure 7). In figure 7, it is seen that the main chains of Mn (II) and Co (II) coordination polymers remain decompose until 900 °C and the main chains of Ni (II) coordination polymers begin to degrade after 500 ° C. We can conclude that the Ni (II) salts exhibit catalytic activity in the degradation of the s-triazine polymer chains.
3.4. Interpretation of Mass Spectra (ESI-MS) of Ligands and All Complexes Electron spray ionization method was used to take the mass spectra of the ligands III and V and polymeric complexes IX and XIII (Figure 8 and Figure 9). The peaks observed at m/z = 327.96 (100%) in the mass spectrum of III, and at m/z = 440.04 (100%) in the mass spectrum of V are the molecular weight of III and V, respectively (Figure 8). As seen from the mass spectra of the polymeric complexes (IX and XIII), the specific peaks are located at m/z = 404.85 (48%) and m/z = 416.91 (85%) for IX; m/z = 404.78 (79%) and m/z = 419.96 (73%) for XIII. The molecular fragments corresponding to these peaks are given in Figure 9. The average molecular weights of the polymers (IX-XIV) were determined as 0.683, 0.680, 0.818, 0.774, 0.781 and 0.738, respectively, measuring their viscosities by the Ostwald viscometer. Using polystyrene as standard [61], the total molecular weights of these polymer complexes were determined according to the equation ŋ = kµα, where µ is the molecular weight, k and α constants were considered as 1.7 x 10-4 and 0.78 according to the previous studies [61, 75, 76]. Because of the usage of polystyrene as standard, the actual molecular weight values might be slightly higher than observed. The reason of the detected values to be lower is the fact that the polymers have a spherical type structure, also supported by other studies [61]. The average molecular weights of the polymeric complexes we obtained by this method were 41720, 41550, 52620, 49000, 49600 and 46050 g/mol for IX-XIV, respectively. According to these data, it was concluded that polymeric complex of Mn(II) consists of 66 and 69 monomer units, respectively, polymeric complex of Co(II) and Ni(II) also consists of 75 to 78 monomer units [61, 75, 76]. Mn (II) polymeric complexes are composed of relatively less monomeric units because their paramagnetic characters are relatively higher than the others. We think that
11
monomer units are more difficult to approach owing to their more paramagnetic characters and thus make the polymerization relatively difficult.
3.5. Interpretation of Effective Magnetic Moment (µeff) Measurements of All Complexes Information on the geometries of the monomer and polymer complexes synthesized in this study was obtained via their effective magnetic moments (µ eff) which were measured at 25 °C. The proposed structures of the monomeric and polymeric complexes were supported with magnetic measurements (Table 1). Monomeric complexes (VI, VII and VIII) of bis(oxirane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate were determined as paramagnetic with d5, d7 and d8 metal ion electron arrangement . Their effective magnetic moment (µ eff) values were determined as follows: 5.84, 3,82 and 2.79 B.M. for Mn(II), Co(II) and Ni(II) ions in t2g3eg2, t2g5eg2 and t2g5eg3, electronic arrangement, respectively. Polymeric complexes (IX, X, XI, XII, XIII and XIV) of bis(oxirane-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate
were
determined
as
paramagnetic with d5, d5, d7, d7, d8 and d8 metal ions electron arrangement. Their effective magnetic moment (µ eff) values were determined as follows: 5.76, 5.78, 3.77, 3.79, 2.75 and 2.76 B.M for each Mn(II), Co(II) and Ni(II) ions in t2g3eg2, t2g3eg2, t2g5eg2, t2g5eg2 and t2g5eg3, t2g5eg3, electronic arrangement, respectively. Accordingly, these monomeric and polymeric complexes seem to have distorted octahedral structures [58-61, 65-74, 77].
3.6. Interpretation of Ultraviolet Visible (UV-Vis) Spectra of Some Complexes In our study, uv-vis spectra (in the range of 200-800 nm) of some of the monomeric and polymeric complexes in ethanol media were obtained in order to explain the geometric structure of them. Considering these spectra; the Uv bands observed in the wavelengths of 237; 232; 228; 219; 234; 219-241 nm belong to π → π* electronic transitions for VI; IX; XI; XII; XIII and XIV monomeric and polymeric complexes, respectively, whereas the Uv bands in the wavelengths of 283; 279; 283; 279; 263, 282; 284; 297 nm belong to n → π* electronic transitions for VI; VIII; IX; XI; XII; XIII and XIV monomeric and polymeric complexes, respectively. In addition, the Uv bands observed in the wavelengths of 316 (π→eg); 318 (π→eg); 362 (π→t2g); 316 (π→eg); 339 (π→t2g) nm belong to Ligand→Metal charge
12
transfer transitions for compounds VI; IX; XII; XIII and XIV respectively. The charge transfer transitions for each complex has multiple values since different donor atoms are coordinated to the central atom. Thus, these complexes are evaluated to be in the distorted octahedral structure. These values are also in agreement with the literature [63, 72, 77, 78]. Since the manganese (II) ion has the high spin electronic arrangement d5 in the octahedral field, ligand field transitions cannot be observed in Mn (II) complexes. These ligand field electronic transitions were observed in visible region as follows: 3T2g → 3T1g(F) at 789, 3
T2g → 3T1g(P) at 577, 3A2g → 3T1g(F) at 666,3A2g → 3T1g(P) at 496 for VIII; 4T2g → 4A2g
at 756 4T2g → 4T1g(P) 605, 4T1g(F) → 4A2g at 694, 4T1g(F)→ 4T1g(P) at 436 for XI; 4T2g → 4
A2g at 757, 4T2g → 4T1g(P) at 563, 4T1g(F) → 4A2g at 694, 4T1g(F)→ 4T1g(P) at 433 for XII;
3
T2g → 3T1g(F) at 686, 3T2g → 3T1g(P) at 528, 3A2g → 3T1g(F) at 610, 3A2g → 3T1g(P) at 400
for XIII; 3T2g → 3T1g(F) 750, 3T2g → 3T1g(P) 524, 3A2g → 3T1g(F) 440, 3A2g → 3T1g(P) 408 for XIV (Figure S4-Figure S10). These ligand field electronic transitions proved that Co(II) and Ni(II) ions were coordinated in octahedral field. These findings were also supported by the magnetic moment measurements.
4. CONCLUSION In this work, a novel monomeric ligand, its mononuclear complexes and their polymer complexes which were the first examples of them coordinated by epoxy groups to the Mn(II), Co(II) or Ni(II) centers were synthesized. The structure of ligands, monomers and polymers were characterized using 1H-NMR and
13
C-NMR, FTIR, ESI-MS, UV-vis
spectrophotometers, TGA and elemental analyses. It was determined that these polymeric complexes (with Mn2+ and Co2+) are thermally stable complexes until 900 °C, but for the others (i.e. with Ni2+) until 500 °C. It was concluded that the Ni(II) salts have a catalytic effect on the degradation of s-triazine polymer chains. All metal ions in the complexes were determined to be octahedral structures with d5 (S = 5/2) (for Mn(II) complexes), d7 (S = 3/2) (for Co(II) complexes) and d8 (S = 1) (for all Ni(II) complexes) according to their magnetic moment values. It was determined that polymeric complexes of Mn(II) consist of 66 and 69 monomer units, respectively, and polymeric complexes of Co(II) and Ni(II) also consist of 75 to 78 monomer units according to the results of viscosity measurement.
13
5. CONFLICT OF INTEREST The authors declare that there is no conflict of interest related to this work.
6. ACKNOWLEDGEMENT This study was produced from Neslihan Orhan’s M. Sc. Thesis. We acknowledge that this work was financially supported by the Karabuk University Scientific Research Projects Coordinatorship (Project No: KBÜBAP-17-YL-176).
Figure 1. An example of s-triazine-based polymeric complexes containing epoxy and dopamine groups.
14
Figure 2. 1H-NMR spectrum (A) and 1H-NMR (D2O Exchange) (B) spectrum of 5-(4,6dichloro-1,3,5-triazine-2-ylamino)isophtalic acid
Figure 3. 1H-NMR spectrum of bis(oksiran-2-ylmethyl)5-(4,6-dicholoro-1,3,5-triazine-2ylamino)isophtalate
15
Figure 4. 13C-NMR spectrum of 5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalic acid
Figure 5. 13C-NMR spectrum of bis(oksiran-2-ylmethyl)5-(4,6-dicholoro-1,3,5-triazine-2ylamino)isophtalate
16
Figure 6. TGA curves of 5-(4,6-Dichloro-1,3,5-triazine-2-ylamino)isophtalic acid (III), Bis(oxirane-2-ylmethyl)5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate (V), (O,O,O`, O`-bis(oxirane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato) manganez(II) chloride (VI), (O,O,O`,O`-bis(oxyrane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine2-ylamino)isophtalato) cobalt(II) acetate (VII) and (O,O,O`,O`-bis(oxirane-2-ylmethyl)-5(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato) nickel(II) chloride (VIII).
17
Figure 7: TGA curves of 3,4-dihydroxybenzaldehyde (IX, XI and XIII) and or 1,2phenylenediamine (X, XII and XIV) polymers of O,O,O`,O`-bis(oxyrane-2-ylmethyl)-5(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato M(II) halide/acetate
18
Figure 8. ESI-MS spectra of 5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalic acid (III) and bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate (V) ligands
19
Figure 9. ESI-MS spectra of IX and XIII
20
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Q. Fang, X. Ding, X. Wu, L. Jiang, Synthesis and characterization of a novel functional monomer containing two allylphenoxy groups and one S-triazine ring and the properties of its copolymer with 4,4′-bismaleimidodiphenylmethane (BMDPM). Polymer 42 (2001) 7595–7602. Z.E. Koc, H.I. Ucan, Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-tris(2,5dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazin and 2,4,6-tris(4-carboxyphenylimino-4’formylphenoxy)-1,3,5-triazin, Transit. Met. Chem. 32 (2007) 597-602. S. Uysal, H.I. Ucan, The synthesis and characterization of single substitute melamine cored Schiff bases and their [Fe(III) and Cr(III)] complexes, J. Incl. Phenom. Macrocycl. Chem. 68(1) (2010) 165173. S. Uysal, Z.E. Koc, Synthesis and characterization of dopamine substitue tripodal trinuclear [(salen/salophen/salpropen)M] (M=Cr(III), Mn(III), Fe(III) ions) capped s-triazine complexes: Investigation of their thermal and magnetic properties, J. Mol. Struct. 1109 (2016) 119-126. Z.E. Koc, S. Uysal, Synthesis and Characterization of Tripodal Oxy-Schiff base (2,4,6-Tris(4Carboxymethylenephenylimino-4′-formylphenoxy)-1,3,5-triazine) and the Thermal and Magnetic Properties of its Fe(III)/Cr(III) Complexes, J Inorg Organomet Polym 21(3) (2011) 400-406. S. Uysal, Z.E. Koc, S. Celikbilek, H.I. Ucan, Synthesis of star-shaped macro molecular schiff base complexes having melamine cores and their magnetic and thermal behaviors. Synth. Commun. 42(7) (2012) 1033-1044. S. Uysal, H.I. Ucan, The synthesis and characterization of 2,4,6-tris(3,4-dihydroxybenzimino)-1,3,5triazine and its [salen/salophenFe(III)] and [salen/salophen Cr(III)] capped complexes, J. Incl. Phenom. Macrocycl. Chem. 65(3) (2009) 403-409. S. Uysal, H.I. Ucan, The synthesis and characterization of melamine based Schiff bases and its trinuclear [salen/salophenFe(III)] and [salen/salophenCr(III)] capped complexes, J. Incl. Phenom. Macrocycl. Chem. 65(3) (2009) 299-304. S. Uysal, A.N. Kursunlu, The Synthesis and Characterization of Star Shaped Metal Complexes of Triazine Cored Schiff Bases: Their Thermal Decompositions and Magnetic Moment Values, J Inorg Organomet Polym 21(2) (2011) 291-296. Z.E. Koc, Complexes of iron(III) and chromium(III) salen and salophen Schiff bases with bridging 1,3,5-triazine derived multidirectional ligands, J. Heterocyclic Chem. 48(4) (2011) 769-775. S. Uysal, Z.E. Koc, The synthesis and characterization of (MSalen/salophen/saldeta/ salpy) [M=Fe(III) or Cr(III)] capped heteromultinuclear schiff bases-dioxime Ni(II) complexes: Their thermal and magnetic behaviours, J. Mol. Struct.1165 (2018) 14-22. S.S. Mahapatra, N. Karak, s-Triazine containing flame retardant hyperbranched polyamines: synthesis, characterization and properties evaluation, Polym. Degrad. Stab. 92 (2007) 947. C. Gao, D. Yan, Hyperbranched polymers: from synthesis to applications, Prog. Polym. Sci. 29 (2004) 183. B. Isci, S. Uysal, The synthesis and characterization of [M(salen/salophen/saldeta)] [M=Cr(III), Mn(III) or Fe(III)] capped s-triazine cored tripodal trinuclear Schiff bases complexes, J. Incl. Phenom. Macrocycl. Chem. 92 (2018) 281–299. A.B.P. Lever, Charge transfer spectra of transition metal complexes, J. Chem. Educ. 51 (1974) 612616.
24
Highlights •
Monomeric ligand including oxirane group and its polymeric complexes were synthesized.
•
All complexes were characterized with 1H-NMR,
13
C-NMR, ESI-MS, FTIR and UV-Vis
spectroscopies. •
Thermal stabilities of these compounds were investigated with thermogravimetric method.
•
Ni(II) have catalytic effect on the degradation of s-triazine polymer chains were determined.
•
Magnetic moments of all complexes were determined and evaluated as distorted octahedral.
Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
Prof. Dr. Şaban UYSAL Corresponding Author
S0022-2860(19)31479-6
DOI:
https://doi.org/10.1016/j.molstruc.2019.127370
Reference:
MOLSTR 127370
To appear in:
Journal of Molecular Structure
Received Date: 16 September 2019 Revised Date:
3 November 2019
Accepted Date: 5 November 2019
Please cite this article as: N. Orhan, S. Uysal, The synthesis and characterization of s-Triazine polymer complexes containing epoxy groups, Journal of Molecular Structure (2019), doi: https://doi.org/10.1016/ j.molstruc.2019.127370. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
The Synthesis and Characterization of s-Triazine Polymer Complexes Containing Epoxy Groups Neslihan ORHAN1 and Saban UYSAL2* 1
University of Karabuk, Institue of Natural and Applied Sciences, Department of Polymer
Engineering, 78050 KARABUK- TURKEY 2
University of Karabuk, Faculty of Science, Department of Chemistry, 78050 KARABUK-
TURKEY *Corresponding Author: ph: +9 (0532) 303 30 35 e-mail: [email protected]
It has been synthesized in this study that s-triazine based monomeric complexes including epoxy groups and their polymeric structures. For this reason, cyanuric chloride (I) has been used as starting material. 5-(4,6-dicholoro-2-1,3,5-triazine-2-ylamino)isophtalic acid coded as “III” has been obtained from the reaction of 5-aminoisophtalic acid II and I at -5 ºC with sodium bicarbonate in aqua/acetone media. Bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5triazine-2-ylamino)izophtalate coded as “V” was synthesized from the reaction of epichlorohydrin (IV) and III in aqua/acetone media with KOH at +2 ºC. In aqua/ethanol media at 60 ºC, monomeric metal complexes (VI, VII and VIII) were obtained from the reaction of V and/or Mn+2, Co+2 and Ni+2. s-Triazine based polymeric metal complexes (IX-XIV) were obtained from the reaction of the monomeric metal complexes and 3,4dihydroxybenzaldehyde/o-phenylenediamine in 1,4-diaxane media with DIPEA at 60 ºC. The structure of ligands, monomers and polymers were characterized using 1H-NMR and 13
C-NMR, FTIR, ESI-MS, UV-vis spectrophotometers, TGA and elemental analyses.
Metal contents in the prepared monomeric and polymeric complexes were determined by inductively coupled plasma atomic emission spectrophotometer (ICP-AES). Magnetic behaviors of the synthesized novel monomeric and polymeric complexes were also investigated. And, these compounds were determined to be high-spin distorted octahedral Mn(II), distorted octahedral Co(II) and distorted octahedral Ni(II).
Keywords: epoxy, oxirane, complex, epichlorohydrin, s-triazine, polymer.
1
1.
Introduction s-Triazine compounds are used as the ligand in coordination chemistry. They also act
as various chelating agents for the synthesis of metal complexes having interesting molecular and supramolecular structures [1-3]. s-Triazine polymers are also used for metal ion extraction [4, 5]. 1,3,5-Triazine-containing ligands are stable molecules even at above the temperature of 150 °C. They only undergo hydrolysis in the presence of concentrated mineral acids via thermal treatments [6]. In recent years, researchers have focused the synthesis of linear magnetic polymers based on s-triazine compounds due to their importance in industrial applications [7] and their potential applications in data storage and quantum computing devices [8-13]. Also, these s-triazine derivatives are important heterocyclic compounds for potential applications in pharmaceutical and biological treatments [14-21]. s-Triazine compounds are also used in various industries including plastic [22], paper [23, 24], electrical [25, 26], textile [27, 28], dye [23, 24], purification [29-33] and telecommunication system [34-38]. Moreover, these compounds have been widely used for the fabrication of light detecting optical switches and image recorders [39-43], production of flame retardant materials with low toxicity [44, 45] and an alternative to some petrochemical raw materials [46-57].
In previous works, dendrimer s-triazine complexes [58,59], linear [M(salen/salophen)] capped s-triazine-based polymeric complexes [60,61] have also been studied. Via their oxygen atoms, epoxy groups can be bonded to the metal atoms. It is seen in the literature that the oxirane group was coordinated from the axial position(s) to the central atoms of the chelates which are in the square planar and square pyramidal forms. [62]. In another previous work, linear [M(salen/salophen)] capped s-triazine-based polymeric complexes containing epoxy and dopamine groups have also been studied (Figure 1) [63]. In the present work, epoxy containing s-triazine polymer complexes were synthesized using cyanuric chloride as starting material. The s-triazine derivatives are usually synthesized using cyanuric chloride owing to the practical exchange of chlorine atoms with temperature. Substituted s-triazine derivative was produced by reaction between 5aminoisophtalic acid and 2,4,6-trichloro-1,3,5-triazine, where the chloride was substituted by the amine group. The acidic -OH groups of the product were treated with epichlorohydrin, and monomer ligand that contains two epoxy groups were obtained. This
2
ligand was reacted with MX2.4H2O (M= Mn(II), Co(II) and Ni(II); X = Cl- and CH3COO-) to form monomer complexes which were polymerized with 1,2-phenylenediamine and 3,4dihydroxybenzaldehyde such that polymeric complexes were obtained. The thermal behaviors of these polymers were investigated in the temperature range of 50-900 °C. Then, the magnetic susceptibility values of these polymers were measured. Finally, Uv-Vis spectra of some of them were taken in range of 200-800 nm.
2.
Experimental
2.1. Reagents and solvents Together with epichlorohydrin and all the solvents, cyanuric chloride (1), 5aminoisophtalic acid, 3,4-dihydroxybenzaldehyde and o-phenylenediamine were bought from Sigma and they were used without further purification. The 1H NMR and
13
C NMR
spectra of the compounds were taken with an Agilent NMR VNMRS spectrometer at 400 MHz and 100 MHz, respectively, through their dimethylsulfoxide (DMSO-d6) solutions. The internal standard of the NMR measurements was tetramethylsilane (TMS). IR spectra were measured by a Thermo SCIENTIFIC NICOLET IS5 FT-IR spectrometer using the ID5 ATR Polarization Accessory (4000–440 cm−1). Thermogravimetric Analysis (TGA) were performed using Hitachi STA7300 Thermal Analysis System. Elemental analyses were performed on a Leco 932 CHNS instrument where the results were in good agreement with the theoretical values. The metal contents of each complex were determined on a Varian, Vista AX CCD Simultaneous model Inductively coupled plasma atomic emission spectrophotometer (ICP-AES). Using ethyl alcohol and chloroform as solvents, the mass spectra were measured in a Thermo TSQ Quantum Access Max LCMS/MS spectrometer. Melting points were determined using an Electro Thermal IA9000 system, while the pH values were obtained from a Milwaukee Mi 150 pH meter. Magnetic moment values of the metal complexes were determined with a Sherwood Scientific MX Gouy magnetic susceptibility apparatus using the Gouy method with Hg[Co(SCN)4] as calibrant. The effective magnetic moments per metal atom, µeff, were calculated using the well-known formula µ eff = 2.84(XMT)1/2 B.M., where XM is the molar susceptibility.
3
2.2. Synthesis of 5-(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalic acid (III)
A solution of natrium bicarbonate (NaHCO3) (0.84 g, 10.00 mmol) in 20 mL water was added to a solution of cyanuric chloride (1.84 g 10,00 mmol) in 20 mL acetone for 15 minutes as stirring continuously at -5 ºC. After 30 minutes, 5-aminoisophtalic acid (1,81 g, 10,00 mmol) in 20 mL acetone, which is stirring for 10 minutes at room temperature, was added to the first solution for 30 minutes as stirring continuously. And, then it was stirred for 2 hrs. at -5 ºC. A solution of natrium bicarbonate (NaHCO3) (0.84 g, 10.00 mmol) in 20 mL water was added to this mixture and stirred for 3 hrs. at -5 ºC. Its pH was set to 7.00 with adding 1 M HCl dropwise. This mixture was kept at 4 ºC for 12 hrs. and filtered under vacuum. The solid white product was also filtered and washed with diethyl ether, and then it was put into a vacuum cabinet for drying. Finally, the products were purified using column chromatography (ethylacetate/n-hexane - 1/3 v/v) (Scheme 1). The characteristic FT-IR bands (cm−1) of (III); (C=Ntrz) 1625; (C-Har) 3125, 3150; (C=O) 1666; (C-Car) 1451, 1568; (N-H) 3391str, 1510bend; (COO) 1371; (OH) 3287 2.3.
Synthesis of bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izoph talate (V)
5-(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalic acid (0,99 g, 3,00 mmol) was solved in 20 mL acetone, and cooled to 2 °C. KOH (0,34 g, 6,00 mmol) in 20 mL aqua was added to the solution. After 30 minutes, epichlorohydrin (0,52 mL, 6,00 mmol) in 20 mL acetone was added drop by drop to the first solution stirring at 2 °C for 15 minutes. The solution was stirred for 3 hours at the same temperature. Finally, the pH of the system was adjusted to around 7.00 with 1.00 M HCl. The mixture was allowed to mature in cooler for 12 hours. The yellow solid formed was washed with 10 ml of diethylether, filtered quickly and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of (V); (C=Ntrz) 1622; (C-Har) 3285(broad); (CHaliph) 2910, 2970, 2805; (C=O) 1667; (C-Car) 1564, 1482; (N-H) 3370str, 1510bend; (COO) 1362; (Oxirane) 1275, 900
4
2.4. Synthesis of monomeric M(II) complexes (M = Mn2+, Co2+ and Ni2+) of bis(oxiran-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate (VI, VII and VIII)
1 mmol of MnCl2.4H2O/Co(CH3COO)2.4H2O/NiCl2.6H2O in 10 mL aqua were added to bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate (V) (0,44g, 1,00 mmol) in 10 mL ethanol at 60 ºC. The solution was stirred for 3 hours at the same temperature. After 2 hrs., the pH of the system was adjusted to around 5.50 with 1.00 M KOH. The solution was stirred for 3 hours at 60 ºC. The mixtures were allowed to mature at room temp. for 12 hours. Light brown, light purple and light green colored precipitates, respectively are rapidly filtered, washed with 10 mL of diethylether and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of monomeric complexes (VI–VIII); (VI): (C=Ntrz) 1622; (C-Har) 3131(broad); (C-Haliph) 2831, 2903; (C=O) 1738; (C-Car) 1557; (N-H) 1278str, 1510bend; (COO) 1364; (Oxirane) 1296, 900 - (VII): (C=Ntrz) 1622; (C-Harom) 3272(broad); (C-Haliph) 3272(broad); (C=O) 1734; (C-Car) 1557; (N-H) 3272str (broad), 1511bend; (COO) 1359; (Oxirane) 1319, 897 - (VIII): (C=Ntrz) 1621; (C-Harom) 3278(broad); (C-Haliph) 2903, 2838; (C=O) 1734; (C-Car) 1557; (N-H) 3278str (broad), 1514bend; (COO) 1362; (Oxirane) 1320, 899 2.5. Synthesis of polymeric M(II) complexes (M = Mn2+, Co2+ and Ni2+) of bis(oxiran-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)izophtalate
VI/VII/VII (1,00 mmol, 0,57/0,62/0,57 g) were solved in 20 mL 1,4-dioxan at 60 ºC. 3,4-dihydroxybenzaldehyde/o-phenylenediamine (0,14/0,11 g, 1,00/1,00 mmol) in 20 mL 1,4-dioxan were added to the first solutions stirring at 60 ºC. Then, N,Ndiisopropylethylamine (0,17 mL, 1,00mmol) were added to these mixture. The reactions were terminated after 48 hours. These products were allowed to mature at room temperature, washed with 10 mL diethylether and dried in vacuo (Scheme 1). The characteristic FT-IR bands (cm−1) of polymeric complexes (IX–XIV); (IX): (C=Ntrz) 1621; (C-Harom) 3138; (C-Haliph) 2980, 2950, 2880, 2827; (C=O) 1745, 1660; (C-Car) 1557, 1563; (N-H) 3277str,1512bend; (COO) 1361; (C-OPhen) 1260; (Oxirane) 1293, 900- (X): (C=Ntrz) 1622; (C-Harom) 3120(broad); (C-Haliph) 2807, 2882; (C=O) 1745;
5
(C-Car) 1557, 1563; (N-H) 3271str, 1510bend; (COO) 1360; (Oxirane) 1261, 900 - (XI): (C=Ntrz) 1622; (C-Harom) 3119(broad); (C-Haliph) 2950, 2884, 2825; (C=O) 1662, 1745; (CCar) 1557, 1563; (N-H) 3285str,1513bend; (COO) 1361; (C-OPhen) 1294; (Oxirane) 1262, 899 - (XII): (C=Ntrz) 1622; (C-Harom) 3138(broad); (C-Haliph) 2825, 2882 (C=O) 1745; (CCar) 1563; (N-H) 3275str
(broad),
1511bend; (COO) 1361; (Oxirane) 1261, 900 - (XIII):
(C=Ntrz) 1621; (C-Harom) 3119(broad); (C-Haliph) 2825, 2882; (C=O) 1741, 1682; (CCar)1556, 1563; (N-H) 3275str
(broad),
1514bend; (COO) 1361; (C-OPhen) 1292; (Oxirane)
1256, 899 - (XIV): (C=Ntrz) 1622; (C-Harom) 3138(broad); (C-Haliph) 2812, 2882; (C=O) 1663; (C-Car) 1512, 1558; (N-H) 3275str
(broad),
1514bend; (COO) 1365; (Oxirane) 1260,
900.
3. RESULTS AND DISCUSSIONS In this study, 2,4,6-trichloro-1,3,5-triazine was used as the starting material. In the presence of sodium bicarbonate in acetone medium, 5-(4,6-dichloro-1,3,5-triazine-2ylamino)isophthalic acid (III) was obtained from the reaction of cyanuric chloride with 5aminoisophthalic acid at -5 ° C. Fujiwara test was performed to confirm that the reaction was unidirectional and the result was evaluated as positive [64]. In the presence of KOH in acetone/water
medium,
bis(oxiran-2-ylmethyl)5-(4,6-dichloro-1,3,5-triazine-2-
ylamino)iso-phtalate (V) was obtained from the reaction of an equivalent III and two equivalent epichlorohydrin (as using 10% excess of epichlorohydrin) at +2 ° C. These monomer ligands (III and V) were identified using 1H-NMR,
13
C-NMR, FTIR, FT-IR
elemental analysis and ESI-MS analyzes. Monomeric metal (Mn2+, Co2+ and Ni2+) complexes (VI, VII and VIII) were obtained from the reaction of bis(oxiran-2-ylmethyl)5(4,6-dicholoro-1,3,5-triazine-2-ylamino)isophtalate
with
MnCl2.4H2O,
Co(CH3COO)2.4H2O and/or NiCl2.6H2O in ethanol media at 60 °C. Polymeric s-triazine complexes (IX-XIV) including epoxy groups were obtained from the reaction of the monomeric complexes with 3.4-dihydroxybenzaldehyde and/or o-phenylenediamine in the presence of DIPEA in 1,4-dioxan media at 60 °C. The structures of these monomeric and polymeric complexes were also identified using FTIR, elemental analysis, ESI-MS, TGA and magnetic susceptibility analysis (Table 1). The polymerization degree of the polymers was determined by the molecular weight determination study with the viscometer.
6
Scheme 1: The synthetic route of ligand, monomeric and polymeric complexes.
3.1. Interpretation of 1H-NMR and 13C-NMR Spectra of Ligands When investigated 1H NMR spectra of III and V obtained as target ligands, for III a singlet was observed at δ=6.970 (2Ha) ppm for seconder -NH2+- group linked to s-triazine ring owing to proton migration from the acid group to the amine group, a singlet was observed at δ=8.166 (2Hb) ppm, a singlet was observed at δ=8.364 (2Hc) ppm for aromatic C-H group, and four singlets were observed between δ=10.588-11.344 (Hd and He) ppm for acidic OH groups. The reason why acidic hydrogens are observed in the spectrum is due to the fact that these hydrogens can see different environments and at the same time they are remote bond interactions (Figure 2A).
7
Table 1: The elemental analysis data and physical properties of all ligands and complexes. [Emprical Formula] (Compound Codes) [C11H6N4O4Cl2] (III) [C17H14N4O6Cl2] (V) [C17H14N4O6Cl4Mn] (VI) [C21H20N4O10Cl2Co] (VII) [C17H14N4O6Cl4Ni] (VIII) [C24H18N4O9Cl2Mn]n (IX) [C23H20N6O6Cl2Mn]n (X) [C28H24N4O13Co]n (XI) [C27H26N6O10Co]n (XII) [C24H18N4O9Cl2Ni]n (XIII) [C23H20N6O6Cl2Ni]n (XIV)
µeff (B.M.) 296 K Dia Dia 5.84 3.82 2.79 5.76 5.78 3.77 3.79 2.75 2.76
M.P °C Color
[Mw] Yield %
197* White 265* Yellow 365* Light Brown 415* Light Purple 400* Light Green 395* Dark Green 380* Brown 430* Dark Purple 425* Dark Purple 385* Light Brown 405* Green
[327.98] 84 [440.03] 65 [566.90] 62 [616.99] 65 [569.90] 67 [632.27] 58 [602.29]n 55 [683.44]n 52 [653.46]n 57 [636.02]n 59 [606.04]n 60
C 40.15 40.12 46.284 6.15 36.01 35.94 40.80 40.74 35.77 35.73 45.59 45.54 45.87 45.83 49.21 49.15 49.63 49.54 45.32 45.25 45.58 45.49
Contents (%) Calculated/Found H N 1.84 17.02 1.83 16.96 3.20 12.70 3.18 12.66 2.49 9.88 2.47 9.85 3.26 9.06 3.23 9.05 2.47 9.82 2.45 9.81 2.87 8.86 2.84 8.84 3.35 13.95 3.31 13.90 3.54 8.20 3.51 8.16 4.01 12.86 3.98 12.77 2.85 8.81 2.84 8.80 3.33 13.87 3.30 13.80
M** 9.69 9.66 9.53 9.50 10.28 10.25 8.69 8.65 9.12 9.10 8.62 8.60 9.02 9.00 9.23 9.21 9.68 9.65
Bold elemental analysis values are found values, M.P = Melting point, *Decomposition Point, **M = Mn(II), Co(II) and Ni(II), µeff = Effective Magnetic Moment.
After the deuterium exchange, disappearing the peaks for acidic group between δ=10.588-11.344 ppm, and at δ=6.970 ppm observed as broad slightly for NH2+ group, and observing a singlet at δ=6.002 (1H) ppm for seconder NH group are a good evidence of formation of the ligand III (Figure 2B). Similarly, disappearing the peaks for acidic group between δ=10.588-11.344 ppm, and observing a dublet at δ=4.421 (4Hd) ppm for the next to oxirane groups, a multiplet at δ=3.138 (2He) ppm for oxirane groups, a dublet at δ=2.285 (4Hf) ppm for oxirane groups are evidence that the original target ligand (V) was obtained (Figure 3) [58, 59, 63, 65]. When the
13
C NMR spectra are examined for (III) and (V), carbon peaks of (III) are
encountered at δ=166.679 ppm for C1, δ=166.262 ppm for C2, δ=154.730 ppm for C7, δ=150.375 ppm for C3, δ=138.290 ppm for C5, δ=132.335 ppm for C4, δ=126.038 ppm for C6, and carbon peaks of (V) are encountered at δ=166.679 ppm for C1, δ=166.262 ppm for C2, δ=154.730 ppm for C7, δ=150.375 ppm for C3, δ=138.290 ppm for C5, δ=132.335 ppm
8
for C4, δ=126.038 ppm for C6, δ=66.481 ppm for C8, δ=49.662 ppm for C9, δ=44.445 ppm for C10. These recorded 13C and 1H resonances are consistent with the literature [58, 59, 63, 65] (Figure 4 and Figure 5).
3.2. Interpretation of FTIR Spectra of Ligand and All Complexes The characteristic FTIR bands for both ligands and all monomeric and polymeric complexes are given in experimental section. The bands at 1666 and 1667 cm-1, 3391 cm-1 and 1510 cm-1 for carbonyl, N-H stretching and N-H bending of ligand III, respectively, have verified that 5-aminoisophtalic acid has attached to s-triazine ring with its N atom. Similarly, which the bands at 1575 cm-1 and 900 cm-1 for oxirane ring stretching and oxirane ring bending of ligand V, respectively, are observed and which the band at 3287 cm-1 for OH groups are disappeared have also verified that epichlorohydrin has attached to carboxylate groups of ligands III. In addition, the observation of the band at 1371 cm-1 for COO bending of ligand III at a lower frequency of ~9 cm-1 for the ligand V also proved that the epichlorohydrin group is attached to the carboxylate groups [58-61, 63, 65-74] (Figure S1, provided as Supporting Information). When examining the FT-IR spectra of the monomer complexes, different from the FTIR spectrum of ligand V, the bands for the carbonyl groups in all the complexes were approximately 71-67 cm-1 at a higher frequency, and the bands for epoxy ring stretching vibrations in all the complexes were approximately 21-44 cm-1 at a higher frequency were observed. These data prove that the ligand V is coordinated to the metal ions (Mn2+, Co2+ and Ni2+) with the carbonyl oxygens and the oxirane oxygens [62, 63] (Figure S1, provided as Supporting Information). Similarly, evaluating the FT-IR spectra of the polymer complexes, characteristic bands of the polymerizing groups unlike the monomer complexes have been observed (Figure S2 and Figure S3, provided as Supporting Information). These bands at 1260 cm-1, 1294 cm-1 and 1291 cm-1 are observed for phenolic stretching vibration of IX, XII and XIII, respectively, and these bands at 1660 cm-1, 1662 cm-1 and 1682 cm-1 are also observed for carbonyl groups of aldehydes, respectively.
9
3.3. Interpretation of TGA Curve of Some of The Complexes Thermal analysis of the ligands, monomeric and polymeric complexes were performed where 1.00 mg sample was heated in a nitrogen atmosphere at the rate of temperature rise 10 °C/min in the range of 50-900 ºC. The weight losses of all complexes determined from the TGA analyses are in good harmony with the calculated values (Table 2). Table 2. Decomposition steps with the temperature range, weight loss and estimated decomposed groups for ligands and all complexes. Compounds [C11H6N4O4Cl2] (III) [C17H14N4O6Cl2] (V) [C17H14N4O6Cl4Mn] (VI) [C21H20N4O10Cl2Co] (VII) [C17H14N4O6Cl4Ni] (VIII) [C24H18N4O9Cl2Mn]n (IX) [C23H20N6O6Cl2Mn]n (X) [C28H24N4O13Co]n (XI) [C27H26N6O10Co]n (XII) [C24H18N4O9Cl2Ni]n (XIII) [C23H20N6O6Cl2Ni]n (XIV)
Step
Temp. range (ºC)
W. Loss (%) Found (Calcd.)
Estimated decomposed group(s) corresponding to weight losses
1 2 1 2 3 1 2 3 1 2 1 2 3 1 2 1 2 1 2 1 2 1 2 1 2
80-320 320-900 80-365 365-445 445-900 95-385 385-481 481-900 73-425 425-900 90-467 467-612 612-827 200-580 580-900 200-580 580-900 200-450 450-815 200-445 445-820 300-500 500-900 300-500 500-900
27.36 (25.53) 46.60 (74.47)* 25.88 (23.12) 19.95 (12.28) 13.70 (64.60)* 14.78 (20.13) 16.22 (15.52) 25.00 (38.08)* 33.63 (37.56) 44.08 (37,65) 40.04 (35.41) 15.14 (13.15) 14.45 (12.44) 31.50 (31.95) 14.00 (44.50)* 31.00 (33.54) 14.15 (41.73)* 30.02 (33.98) 20.03 (23.87) 30.00 (35.54) 22.00 (24.96) 34.80 (31.76) 44.04 (44.23) 35.04 (33.33) 44.02 (41.48)
-carbonate groups -the other organic groups -methyloxiran groups -carbonate groups -the other organic groups -methyloxiran groups -carbonate groups -the other organic groups -methyloxiran and carbonate groups -the other organic groups -methyloxiran and carbonate groups -benzene in the remaining structure -chlorine atoms -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network -methyloxiran and carbonate groups -organic group on main network
*Decomposition of the compounds could not be completed because heating operation was terminated at 900 °C.
As for TGA curve of ligand, monomeric and polymeric complexes, TGA curve of all compounds have been given in Figure 6 and Figure 7. Weight losses for all complexes, decomposition temperature ranges and estimated decomposed group(s) corresponding to the weight losses have been given in Table 2, particularly. Decomposition of some compounds could not be completed because heating operation was terminated at 900 °C. It
10
is believed that metal salts and s-triazine rings remain at 900 ° C without degradation (Figure 6 and Figure 7). In figure 7, it is seen that the main chains of Mn (II) and Co (II) coordination polymers remain decompose until 900 °C and the main chains of Ni (II) coordination polymers begin to degrade after 500 ° C. We can conclude that the Ni (II) salts exhibit catalytic activity in the degradation of the s-triazine polymer chains.
3.4. Interpretation of Mass Spectra (ESI-MS) of Ligands and All Complexes Electron spray ionization method was used to take the mass spectra of the ligands III and V and polymeric complexes IX and XIII (Figure 8 and Figure 9). The peaks observed at m/z = 327.96 (100%) in the mass spectrum of III, and at m/z = 440.04 (100%) in the mass spectrum of V are the molecular weight of III and V, respectively (Figure 8). As seen from the mass spectra of the polymeric complexes (IX and XIII), the specific peaks are located at m/z = 404.85 (48%) and m/z = 416.91 (85%) for IX; m/z = 404.78 (79%) and m/z = 419.96 (73%) for XIII. The molecular fragments corresponding to these peaks are given in Figure 9. The average molecular weights of the polymers (IX-XIV) were determined as 0.683, 0.680, 0.818, 0.774, 0.781 and 0.738, respectively, measuring their viscosities by the Ostwald viscometer. Using polystyrene as standard [61], the total molecular weights of these polymer complexes were determined according to the equation ŋ = kµα, where µ is the molecular weight, k and α constants were considered as 1.7 x 10-4 and 0.78 according to the previous studies [61, 75, 76]. Because of the usage of polystyrene as standard, the actual molecular weight values might be slightly higher than observed. The reason of the detected values to be lower is the fact that the polymers have a spherical type structure, also supported by other studies [61]. The average molecular weights of the polymeric complexes we obtained by this method were 41720, 41550, 52620, 49000, 49600 and 46050 g/mol for IX-XIV, respectively. According to these data, it was concluded that polymeric complex of Mn(II) consists of 66 and 69 monomer units, respectively, polymeric complex of Co(II) and Ni(II) also consists of 75 to 78 monomer units [61, 75, 76]. Mn (II) polymeric complexes are composed of relatively less monomeric units because their paramagnetic characters are relatively higher than the others. We think that
11
monomer units are more difficult to approach owing to their more paramagnetic characters and thus make the polymerization relatively difficult.
3.5. Interpretation of Effective Magnetic Moment (µeff) Measurements of All Complexes Information on the geometries of the monomer and polymer complexes synthesized in this study was obtained via their effective magnetic moments (µ eff) which were measured at 25 °C. The proposed structures of the monomeric and polymeric complexes were supported with magnetic measurements (Table 1). Monomeric complexes (VI, VII and VIII) of bis(oxirane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate were determined as paramagnetic with d5, d7 and d8 metal ion electron arrangement . Their effective magnetic moment (µ eff) values were determined as follows: 5.84, 3,82 and 2.79 B.M. for Mn(II), Co(II) and Ni(II) ions in t2g3eg2, t2g5eg2 and t2g5eg3, electronic arrangement, respectively. Polymeric complexes (IX, X, XI, XII, XIII and XIV) of bis(oxirane-2ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate
were
determined
as
paramagnetic with d5, d5, d7, d7, d8 and d8 metal ions electron arrangement. Their effective magnetic moment (µ eff) values were determined as follows: 5.76, 5.78, 3.77, 3.79, 2.75 and 2.76 B.M for each Mn(II), Co(II) and Ni(II) ions in t2g3eg2, t2g3eg2, t2g5eg2, t2g5eg2 and t2g5eg3, t2g5eg3, electronic arrangement, respectively. Accordingly, these monomeric and polymeric complexes seem to have distorted octahedral structures [58-61, 65-74, 77].
3.6. Interpretation of Ultraviolet Visible (UV-Vis) Spectra of Some Complexes In our study, uv-vis spectra (in the range of 200-800 nm) of some of the monomeric and polymeric complexes in ethanol media were obtained in order to explain the geometric structure of them. Considering these spectra; the Uv bands observed in the wavelengths of 237; 232; 228; 219; 234; 219-241 nm belong to π → π* electronic transitions for VI; IX; XI; XII; XIII and XIV monomeric and polymeric complexes, respectively, whereas the Uv bands in the wavelengths of 283; 279; 283; 279; 263, 282; 284; 297 nm belong to n → π* electronic transitions for VI; VIII; IX; XI; XII; XIII and XIV monomeric and polymeric complexes, respectively. In addition, the Uv bands observed in the wavelengths of 316 (π→eg); 318 (π→eg); 362 (π→t2g); 316 (π→eg); 339 (π→t2g) nm belong to Ligand→Metal charge
12
transfer transitions for compounds VI; IX; XII; XIII and XIV respectively. The charge transfer transitions for each complex has multiple values since different donor atoms are coordinated to the central atom. Thus, these complexes are evaluated to be in the distorted octahedral structure. These values are also in agreement with the literature [63, 72, 77, 78]. Since the manganese (II) ion has the high spin electronic arrangement d5 in the octahedral field, ligand field transitions cannot be observed in Mn (II) complexes. These ligand field electronic transitions were observed in visible region as follows: 3T2g → 3T1g(F) at 789, 3
T2g → 3T1g(P) at 577, 3A2g → 3T1g(F) at 666,3A2g → 3T1g(P) at 496 for VIII; 4T2g → 4A2g
at 756 4T2g → 4T1g(P) 605, 4T1g(F) → 4A2g at 694, 4T1g(F)→ 4T1g(P) at 436 for XI; 4T2g → 4
A2g at 757, 4T2g → 4T1g(P) at 563, 4T1g(F) → 4A2g at 694, 4T1g(F)→ 4T1g(P) at 433 for XII;
3
T2g → 3T1g(F) at 686, 3T2g → 3T1g(P) at 528, 3A2g → 3T1g(F) at 610, 3A2g → 3T1g(P) at 400
for XIII; 3T2g → 3T1g(F) 750, 3T2g → 3T1g(P) 524, 3A2g → 3T1g(F) 440, 3A2g → 3T1g(P) 408 for XIV (Figure S4-Figure S10). These ligand field electronic transitions proved that Co(II) and Ni(II) ions were coordinated in octahedral field. These findings were also supported by the magnetic moment measurements.
4. CONCLUSION In this work, a novel monomeric ligand, its mononuclear complexes and their polymer complexes which were the first examples of them coordinated by epoxy groups to the Mn(II), Co(II) or Ni(II) centers were synthesized. The structure of ligands, monomers and polymers were characterized using 1H-NMR and
13
C-NMR, FTIR, ESI-MS, UV-vis
spectrophotometers, TGA and elemental analyses. It was determined that these polymeric complexes (with Mn2+ and Co2+) are thermally stable complexes until 900 °C, but for the others (i.e. with Ni2+) until 500 °C. It was concluded that the Ni(II) salts have a catalytic effect on the degradation of s-triazine polymer chains. All metal ions in the complexes were determined to be octahedral structures with d5 (S = 5/2) (for Mn(II) complexes), d7 (S = 3/2) (for Co(II) complexes) and d8 (S = 1) (for all Ni(II) complexes) according to their magnetic moment values. It was determined that polymeric complexes of Mn(II) consist of 66 and 69 monomer units, respectively, and polymeric complexes of Co(II) and Ni(II) also consist of 75 to 78 monomer units according to the results of viscosity measurement.
13
5. CONFLICT OF INTEREST The authors declare that there is no conflict of interest related to this work.
6. ACKNOWLEDGEMENT This study was produced from Neslihan Orhan’s M. Sc. Thesis. We acknowledge that this work was financially supported by the Karabuk University Scientific Research Projects Coordinatorship (Project No: KBÜBAP-17-YL-176).
Figure 1. An example of s-triazine-based polymeric complexes containing epoxy and dopamine groups.
14
Figure 2. 1H-NMR spectrum (A) and 1H-NMR (D2O Exchange) (B) spectrum of 5-(4,6dichloro-1,3,5-triazine-2-ylamino)isophtalic acid
Figure 3. 1H-NMR spectrum of bis(oksiran-2-ylmethyl)5-(4,6-dicholoro-1,3,5-triazine-2ylamino)isophtalate
15
Figure 4. 13C-NMR spectrum of 5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalic acid
Figure 5. 13C-NMR spectrum of bis(oksiran-2-ylmethyl)5-(4,6-dicholoro-1,3,5-triazine-2ylamino)isophtalate
16
Figure 6. TGA curves of 5-(4,6-Dichloro-1,3,5-triazine-2-ylamino)isophtalic acid (III), Bis(oxirane-2-ylmethyl)5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate (V), (O,O,O`, O`-bis(oxirane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato) manganez(II) chloride (VI), (O,O,O`,O`-bis(oxyrane-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine2-ylamino)isophtalato) cobalt(II) acetate (VII) and (O,O,O`,O`-bis(oxirane-2-ylmethyl)-5(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato) nickel(II) chloride (VIII).
17
Figure 7: TGA curves of 3,4-dihydroxybenzaldehyde (IX, XI and XIII) and or 1,2phenylenediamine (X, XII and XIV) polymers of O,O,O`,O`-bis(oxyrane-2-ylmethyl)-5(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalato M(II) halide/acetate
18
Figure 8. ESI-MS spectra of 5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalic acid (III) and bis(oxiran-2-ylmethyl)-5-(4,6-dichloro-1,3,5-triazine-2-ylamino)isophtalate (V) ligands
19
Figure 9. ESI-MS spectra of IX and XIII
20
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Highlights •
Monomeric ligand including oxirane group and its polymeric complexes were synthesized.
•
All complexes were characterized with 1H-NMR,
13
C-NMR, ESI-MS, FTIR and UV-Vis
spectroscopies. •
Thermal stabilities of these compounds were investigated with thermogravimetric method.
•
Ni(II) have catalytic effect on the degradation of s-triazine polymer chains were determined.
•
Magnetic moments of all complexes were determined and evaluated as distorted octahedral.
Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
Prof. Dr. Şaban UYSAL Corresponding Author