Synthesis and Characterization of Some New Complexes of Magnesium (II) and Zinc (II) with the Natural Flavonoid Primuletin
Abstract
:1. Introduction
2. Results and Discussion
Compound | DMSO | DMF | AcCN | CHCl3 | MeOH | EtOH |
---|---|---|---|---|---|---|
HL | soluble | soluble | soluble | soluble | soluble at mild heating | soluble at mild heating |
[Mg(L)2(H2O)2]·H2O (1) | soluble | slightly soluble | slightly soluble | soluble at mild heating | slightly soluble | slightly soluble |
[Zn(L)2(H2O)2]·0.5H2O (2) | soluble | soluble | soluble | soluble | slightly soluble | slightly soluble |
Compound | Molecular formula | Molecular weight
(g mol−1) | Anal. found (calcd.) (%) | Molar conductance ΛM (Ω−1 cm2 mol−1) | ||
---|---|---|---|---|---|---|
C | H | M | ||||
[Mg(L)2(H2O)2]·H2O
(1) | MgC30H24O9 | 552.82 | 64.95 (65.18) | 4.24 (4.38) | 4.10 (4.39) | 2 |
[Zn(L)2(H2O)2]·0.5H2O
(2) | ZnC30H23O8.5 | 584.90 | 61.40 (61.60) | 4.12 (3.96) | 10.92 (11.18) | 3.5 |
2.1. IR Spectra
Compound | ν(O-H) | ν(C=O) | ν(C=C) | ν(C-O) + δ(OH) | ν(C-O-C) | γw(H2O) |
---|---|---|---|---|---|---|
HL | 3,200–2,600 b, m | 1,654 s; 1,615 s | 1,587 s | 1,357 m; 1,298 s | 1,255 s | - |
[Mg(L)2(H2O)2]·H2O (1) | 3,600–2,600 b, m | 1,634 s | 1,583 s | 1,361 m; 1,297 w | 1,251 s | 422 w |
[Zn(L)2(H2O)2]·0.5H2O (2) | 3,600–2,600 b, m | 1,632 s | 1,580 s | 1,355 m; 1,297 w | 1,250 s | 546 w |
2.2. UV-Vis Spectra
Compound | λmax (nm) | |
---|---|---|
Band I | Band II | |
HL | 396 | 280 |
[Mg(L)2(H2O)2]·H2O (1) | 406.5 | 284 |
[Zn(L)2(H2O)2]·0.5H2O (2) | 403.5 | 283 |
2.3. 1H-NMR and 13CNMR Spectra
Compound | δ of 1H (J, Hz) | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
H-3 | H-6 | H-7 | H-8 | H-3′ | H-4′ | H-5′ | H-2′ | H-6′ | OH | |
HL | 7.1 (s) | 6.8 (d, 8.3) | 7.6 (t, 8.1) | 7.2 (d, 8.1) | 7.6 (m) | 8.1 (dd, 7.8, 1.7) | 12.55 (s) | |||
(1) | 6.8 (s) | 6.4(bd, 9.9) | 7.3 (t, 8.2) | 6.3 (bd, 8.2) | 7.6 (m) | 8.0 (dd, 8.0, 2.6) | - | |||
(2) | 7.0 (s) | 6.5 (d, 8.4) | 7.4 (t, 8.4) | 6.7 (d, 8.4) | 7.6 (m) | 8.1 (dd, 8.2, 1.7) | - |
Compound | δ of 13C | ||||||||
---|---|---|---|---|---|---|---|---|---|
C-2 | C-3 | C-4 | C-5 | C-6 | C-7 | C-8 | C-9 | C-10 | |
HL | 164.1 | 105.7 | 183.2 | 159.8 | 111.0 | 135.9 | 107.5 | 155.9 | 110.1 |
(1) | 171.4 | 106.2 | 180.9 | 161.1 | 116.9 | 134.9 | 96.8 | 158.2 | 113.4 |
(2) | 171.4 | 106.0 | 183.1 | 162.1 | 117.1 | 135.4 | 99.7 | 157.78 | 112.2 |
Compound | δ of 13C | ||||||||
C-1′ | C-2′ | C-6′ | C-3′ | C-5′ | C-4′ | ||||
HL | 130.53 | 126.6 | 129.2 | 132.3 | |||||
(1) | 131.11 | 126.1 | 129.2 | 131.5 | |||||
(2) | 130.72 | 126.3 | 129.2 | 131.9 |
2.4. Mass Spectra
MLn species | Protonated molecular ion [MLn+H]+ (m/z) | Fragment at 5 eV and 1.5 mTorr argon (m/z) | Type of fragment | Fragmentation |
---|---|---|---|---|
24MgL2 | 499 | 261 | 24MgL+ | [24MgL+H-L]+ |
25MgL2 | 500 | 262 | 25MgL+ | [25MgL+H-L]+ |
26MgL2 | 501 | 263 | 26MgL+ | [26MgL+H-L]+ |
64ZnL2 | 539 | 301 | 64ZnL+ | [64ZnL+H-L]+ |
66ZnL2 | 541 | 303 | 66ZnL+ | [66ZnL+H-L]+ |
68ZnL2 | 543 | 305 | 68ZnL+ | [68ZnL+H-L]+ |
2.5. Thermal Behavior
Complex | Step | Thermal effect | Temperature range/°C | Δmexp/% | Δmcalc/% | Chemical process |
---|---|---|---|---|---|---|
[Mg(L)2(H2O)2]·H2O
(1) | 1. | Endothermic | 52–90 | 3.0 | 3.3 | H2O loss |
2. | Endothermic | 120–160 | 3.1 | 3.3 | H2O loss | |
3. | Endothermic | 170–206 | 3.2 | 3.3 | H2O loss | |
4. | Exothermic | 408–900 | 56.3 | Partial oxidative degradation of organic part | ||
Residue (MgO + organic residue) | 34.4 | |||||
[Zn(L)2(H2O)2]·0.5H2O
(2) | 1. | Endothermic | 54–75 | 1.7 | 1.6 | 0.5 H2O loss |
2. | Endothermic | 85–128 | 6.1 | 6.2 | 2H2O loss | |
3. | Exothermic | 300–750 | 78.5 | 78.3 | Oxidative degradation of organic part | |
Residue (ZnO) | 13.7 | 13.9 |
2.5.1. Thermal Decomposition of [Mg(L)2(H2O)2]·H2O
2.5.2. Thermal Decomposition of [Zn(L)2(H2O)2]·0.5H2O
2.6. Fluorescent Properties
Compound | Excitation wavelength
λexc = 400 nm | Excitation wavelength
λexc = 429 nm | ||
---|---|---|---|---|
Emission wavelength
λem (nm) | Relative fluorescence
intensity (a.u.) | Emission wavelength
λem (nm) | Relative fluorescence
intensity (a.u.) | |
HL | 540 599 | 82.43 174.87 | 456 545 642 | >1000 73.23 323.29 |
[Mg(L)2(H2O)2]·H2O (1) | 545 598 | 510.61 379.94 | 459 548 642 | 824.65 576.89 331.28 |
[Zn(L)2(H2O)2]·0.5H2O (2) | 548 598 | 536.83 410 | 458 548 642 | 727.71 627.11 346.30 |
3. Experimental
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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Uivarosi, V.; Badea, M.; Olar, R.; Drǎghici, C.; Bǎrbuceanu, Ş.F. Synthesis and Characterization of Some New Complexes of Magnesium (II) and Zinc (II) with the Natural Flavonoid Primuletin. Molecules 2013, 18, 7631-7645. https://doi.org/10.3390/molecules18077631
Uivarosi V, Badea M, Olar R, Drǎghici C, Bǎrbuceanu ŞF. Synthesis and Characterization of Some New Complexes of Magnesium (II) and Zinc (II) with the Natural Flavonoid Primuletin. Molecules. 2013; 18(7):7631-7645. https://doi.org/10.3390/molecules18077631
Chicago/Turabian StyleUivarosi, Valentina, Mihaela Badea, Rodica Olar, Constantin Drǎghici, and Ştefania Felicia Bǎrbuceanu. 2013. "Synthesis and Characterization of Some New Complexes of Magnesium (II) and Zinc (II) with the Natural Flavonoid Primuletin" Molecules 18, no. 7: 7631-7645. https://doi.org/10.3390/molecules18077631