Bazı yeni iminooksim-palladyum(II) ve platin(II) komplekslerinin yapısal ve spektroskopik özelliklerinin deneysel ve kuramsal incelenmesi
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Date
2014
Authors
Kaya, Yunus
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Publisher
Uludağ Üniversitesi
Abstract
çalışmada dört yeni iminooksim ligandı, fenil-(1-fenil-etilimino)etanal oksim (ffeieoH), (2-hidroksi-etilimino)-2-fenil-etanal oksim (heifeoH), 2-(hidroksiimino)-1-feniletiliden]asetohidrazon (hifeahH2), (2-hidroksi-etilimino)-naftalin-2-il-etanal oksim (heineoH) ve bu dört ligandın palladyum(II) ve platin(II) iyonları ile oluşturduğu sekiz yeni kompleksi sentezlendi. Ligantların ve komplekslerin yapıları elementel analiz, IR, NMR ve UV-Gör bölge spektroskopi teknikleri ve X-ışını tek kristal kırınım yöntemi ile aydınlatıldı. Ayrıca ligant ve komplekslerin floresans özellikleri araştırıldı. X-ışını kırınımı çalışmaları, ffeieoH ligandının palladyum(II) ve platin(II) tuzları ile EtOH/su ortamında tepkimesi esnasında ligandın hidrolize uğradığını ve hidroliz ürünlerinin yapıya katıldığını gösterdi. HeifeoH ve heineoH ligantlarının palladyum(II) ve platin(II) iyonları ile beklenildiği gibi 1:2 metal:ligant oranında kare düzlem geometride kompleksler oluşturduğu ve ligantların oksim protonunlarını kaybettiği belirlendi. Ayrıca, heifeoH ligandının palladyum(II) kompleksinin iki polimorf kristalleri farklı iki renkte ve şekilde oluştuğu gözlendi. Polimorf kristallerin, X-ışını kristal analizi ile Ci ve C1 nokta gruplarında olduğu belirlendi. Palladyum(II) kompleksinde polimorfizme hidroksietil grubunun farklı konformer yapılarının neden olduğu gözlendi. X-ışını tek kristal analiz sonuçları ile hifeahH2 ligandının palladyum(II) ve platin(II) komplekslerinde, ligandın 1:2 metal:ligant oranında kompleksler oluşturduğu, ligandın birinin oksim diğerinin hidrazin protonunu kaybederek imin ve hidrazin azotlarından metal iyonlarına katılması ile beşli ve altılı iki şelat oluşturduğu belirlendi. Yapısı aydınlatılan ligant ve komplekslerin kuramsal spektroskopik özellikleri (IR, NMR, UV-Görünür bölge ve floresans) incelendi. Tüm hesaplamalar Yoğunluk Fonksiyon Kuramı' na göre yapıldı. Optimizasyon, frekans ve NMR hesaplamalarında, ligantlar için 6-311++G(d,p) ve LANL2DZ taban kümeleri kullanılırken, kompleksler için LANL2DZ taban kümesi seçildi. UV-Gör bölge ve floresans spektrumları ZB-YFK/LANL2DZ yöntem ve taban kümesinde incelendi. Ligantların kuramsal izomer çalışmaları 6-311++G(d,p) taban kümesinde yapıldı. Tek kristali elde edilemeyen heifeoH ligandı için konformer çalışmaları 6-31G(d,p) taban kümesinde yapılarak 1296 molekül arasından en olası geometri belirlendi. Ayrıca hifeahH2 ligandının palladyum(II) ve platin(II) komplekslerinin beş farklı bağlanma izomer çalışması yapıldı. FfeieoH ligandının nötral ve asidik ortamdaki hidroliz mekanizması B3LYP/6-311G(d,p) yöntem ve taban kümesinde çalışıldı. Asidik ortamda yaklaşık 63 kJ/mol daha düşük aktivasyon enerjisi hesaplanan ffeieoH molekülünün hidroliz tepkimesine göre sulu ortamda hidrolize uğrayabileceği belirlendi. Ligant ve komplekslerin normal koordinat analizi çalışmaları ile şiddeti 5' in üzerinde olan tüm titreşim modları işaretlendi. Moleküllerin deneysel UV-Gör bölge spektrumlarından ve kuramsal singlet-singlet enerji hesaplamalarından elektronik geçişlerin ligantlarda π–π*, komplekslerde ise π–π*, metalden-liganda (MLCT) ve liganttan-metale (LMCT) yük aktarım geçişlerinden kaynaklandığı belirlendi. Kompleksler oda sıcaklığında herhangi floresans özellik göstermezken, ffeieoH ve heineoH ligantları zayıf floresans özellik göstermektedir. Kuramsal singlet-triplet enerji hesaplamaları ile de ligantlardaki floresans özelliklerin π–π* geçişlerinden kaynaklandığı belirlendi. Elektronik geçişlere katılan HOMO-LUMO orbitalleri görüntülendi.
In this study, four new imineoxime ligands, phenyl-[(1-phenylethyl)imino]-ethanal oxime (ppeieoH), [(2-hydroxyethyl)imino]-2-phenyl-ethanal oxime (heipeoH), (2-hydroxyethyl)imino-1-phenylethyldene]acetohydrazide (hipeahH2) and (2-hydroxyethyl)-naphtalene-2-yl-ethanal oxime (heineoH), and their palladium(II) and platinum(II) complexes were synthesized. The ligands and their complexes were characterized by elemental analysis, IR, NMR and UV-Vis spectroscopy techniques, and X-ray single crystal diffraction method. Additionally, fluorescence properties of the ligands and complexes were investigated. X-ray diffraction results demonstrated that the ppeieoH ligand hydrolysed during its reaction with the palladium(II) and platinum(II) salts in the EtOH/water solution and the hydrolysed products participated in the structure of the complexes. It was found that the palladium(II) and platinum(II) complexes have a 1:2 metal:ligand ratio and square planar geometry. The ligands lost the oxime protons. Besides, cocrystallization of two polymorphs of the palladium(II) complex of the heipeoH ligand was observed by the different colors and shapes of the crystals. They were identified by X-ray measurements with C1 and Ci point groups. The polymorphism in the palladium(II) complex seems to be due to the orientation of the hydroxyethyl groups. X-ray diffraction results indicated that the palladium(II) and platinum(II) complexes of hipeahH2 have a 1:2 metal:ligand ratio, the hydrazine and oxime protons of different ligands are lost and this result in the coordination of the ligands with five- and six-membered chelates. The theoretical spectroscopic properties (IR, NMR, UV-Vis, fluorescence) of the ligands and complexes were investigated. All the calculations were carried out by Density Functional Theory (DFT). The LANL2DZ basis set was used for calculations of complexes, while the 6-311++G(d,p) and LANL2DZ basis sets for ligands. UV-Vis and fluorescence spectra were studied by the TD-DFT/LANL2DZ method. The 6-311++G(d,p) basis set was applied for the isomer studies of ligands. Conformer studies of heipeoH ligand, which can not be obtained as a single crystal, were carried out with the 6-31G(d,p) basis set, and the geometry of the molecule was determined from those of calculated 1296 molecules. Besides, the studies on the palladium(II) and platinum(II) complexes of hipeahH2 ligand verified that there were five different isomers. Hydrolysis mechanisms of ppeieoH ligand in neutral and acidic solutions were studied using the B3LYP/6-311G(d,p) method. PpeieoH molecule had around 63 kJ/mol lower activation energy in the acidic solution than that in the aqueous solution. Vibration modes of ligands and complexes with higher intensity than 5 were taken into consideration in normal coordinate analysis studies. From experimental UV-Vis spectra and theoretical singlet-singlet energy calculations, electronic transitions were assigned to π–π* transitions for ligands and π–π* transition, metal to ligand (MLCT) and ligand to metal (LMCT) charge transfer for complexes. While complexes presented no fluorescence at room temperature, ffeieoH and heineoH ligands were weakly fluorescent. Theoretical singlet-triplet energy calculations demonstrated that fluorescence properties of ligands were related to π–π* transitions. Participation of HOMO-LUMO orbitals to electronic transitions were displayed.
In this study, four new imineoxime ligands, phenyl-[(1-phenylethyl)imino]-ethanal oxime (ppeieoH), [(2-hydroxyethyl)imino]-2-phenyl-ethanal oxime (heipeoH), (2-hydroxyethyl)imino-1-phenylethyldene]acetohydrazide (hipeahH2) and (2-hydroxyethyl)-naphtalene-2-yl-ethanal oxime (heineoH), and their palladium(II) and platinum(II) complexes were synthesized. The ligands and their complexes were characterized by elemental analysis, IR, NMR and UV-Vis spectroscopy techniques, and X-ray single crystal diffraction method. Additionally, fluorescence properties of the ligands and complexes were investigated. X-ray diffraction results demonstrated that the ppeieoH ligand hydrolysed during its reaction with the palladium(II) and platinum(II) salts in the EtOH/water solution and the hydrolysed products participated in the structure of the complexes. It was found that the palladium(II) and platinum(II) complexes have a 1:2 metal:ligand ratio and square planar geometry. The ligands lost the oxime protons. Besides, cocrystallization of two polymorphs of the palladium(II) complex of the heipeoH ligand was observed by the different colors and shapes of the crystals. They were identified by X-ray measurements with C1 and Ci point groups. The polymorphism in the palladium(II) complex seems to be due to the orientation of the hydroxyethyl groups. X-ray diffraction results indicated that the palladium(II) and platinum(II) complexes of hipeahH2 have a 1:2 metal:ligand ratio, the hydrazine and oxime protons of different ligands are lost and this result in the coordination of the ligands with five- and six-membered chelates. The theoretical spectroscopic properties (IR, NMR, UV-Vis, fluorescence) of the ligands and complexes were investigated. All the calculations were carried out by Density Functional Theory (DFT). The LANL2DZ basis set was used for calculations of complexes, while the 6-311++G(d,p) and LANL2DZ basis sets for ligands. UV-Vis and fluorescence spectra were studied by the TD-DFT/LANL2DZ method. The 6-311++G(d,p) basis set was applied for the isomer studies of ligands. Conformer studies of heipeoH ligand, which can not be obtained as a single crystal, were carried out with the 6-31G(d,p) basis set, and the geometry of the molecule was determined from those of calculated 1296 molecules. Besides, the studies on the palladium(II) and platinum(II) complexes of hipeahH2 ligand verified that there were five different isomers. Hydrolysis mechanisms of ppeieoH ligand in neutral and acidic solutions were studied using the B3LYP/6-311G(d,p) method. PpeieoH molecule had around 63 kJ/mol lower activation energy in the acidic solution than that in the aqueous solution. Vibration modes of ligands and complexes with higher intensity than 5 were taken into consideration in normal coordinate analysis studies. From experimental UV-Vis spectra and theoretical singlet-singlet energy calculations, electronic transitions were assigned to π–π* transitions for ligands and π–π* transition, metal to ligand (MLCT) and ligand to metal (LMCT) charge transfer for complexes. While complexes presented no fluorescence at room temperature, ffeieoH and heineoH ligands were weakly fluorescent. Theoretical singlet-triplet energy calculations demonstrated that fluorescence properties of ligands were related to π–π* transitions. Participation of HOMO-LUMO orbitals to electronic transitions were displayed.
Description
Keywords
İminooksim, Floresans, Palladyum(II), Platin(II), Yoğunluk Fonksiyon Kuramı, IR, NMR, UV-Gör bölge, Imineoxime, Fluorescence, Palladium(II, Platinum(II), Density Functional Theory, UV-Vis
Citation
Kaya, Y. (2014). Bazı yeni iminooksim-palladyum(II) ve platin(II) komplekslerinin yapısal ve spektroskopik özelliklerinin deneysel ve kuramsal incelenmesi. Yayınlanmamış doktora tezi. Uludağ Üniversitesi Fen Bilimleri Enstitüsü.