Synthesis and 1H NMR characterization of novel ru(II) complex

A novel Ru(II) complex has been successfully synthesized. Firstly, the new synthetic ligands composing an anchor 1,10-phenanthroline-5-carboxylic acid (compound D) and an antenna ligand [5-(9,9-dihexylfluoren-2-yl)]-phenanthroline (compound H) were synthesized. After that, novel Ru(II) complex was designed by association of two antenna ligands, one anchor and Ru(II) salt.
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Synthesis and 1H NMR characterization of novel ru(II) complexTẠP CHÍ KHOA HỌC ĐHSP TPHCMSố 12(90) năm 2016____________________________________________________________________________________________________________SYNTHESIS AND 1H NMR CHARACTERIZATIONOF NOVEL Ru(II) COMPLEXBUI XUAN VUONG*ABSTRACTA novel Ru(II) complex has been successfully synthesized. Firstly, the new syntheticligands composing an anchor 1,10-phenanthroline-5-carboxylic acid (compound D) andan antenna ligand [5-(9,9-dihexylfluoren-2-yl)]-phenanthroline (compound H) weresynthesized. After that, novel Ru(II) complex was designed by association of two antennaligands, one anchor and Ru(II) salt. All compounds in these synthetic steps were analyzedby 1H NMR spectra and elemental analysis.Keywords: Ru(II) complex; antenna ligands; anchor; luminescence; quantum dot.TÓM TẮTTổng hợp và đặc trưng bằng phổ 1H NMR phức chất mới của Ru(II)Một hợp chất phức mới của Ru(II) đã được tổng hợp thành công. Trước tiên, cácphối tử mới gồm phối tử móc (móc liên kết) 1,10-phenanthroline-5-carboxylic axít (hợpchất D) và phối tử tín hiệu [5-(9,9-dihexylfluoren-2-yl)]-phenanthroline (hợp chất H) đượcđiều chế. Sau đó, phức mới của Ru(II) được tạo ra bằng các phản ứng kết hợp giữa cácphối tử và hợp chất muối Ru(II). Các hợp chất trong quá trình tổng hợp được đặc trưngbằng phổ 1H NMR và phương pháp phân tích nguyên tố.Từ khóa: phức Ru(II), phối tử tín hiệu, phối tử móc, anchor, phát quang, chấm lượng tử.1.IntroductionRuthenium has several oxidation states: Ru(II), Ru(III), and Ru(IV). Most ofthese oxidation states are accessible under physiological conditions.Recent literature present the use of ruthenium(IV) complexes as a catalyst or precatalyst. Allylic ruthenium(IV) complexes as pre-catalyst in transition metal-catalyzedreactions. The most domination is in the nucleophilic substitution reactions, where theyappear either as initial catalysts or are generated upon oxidative addition of allylicsubstrates to ruthenium(II) pre-catalysts [1]. Whereas, bis(allyl) ruthenium(IV)complexes containing water-soluble phosphane ligands can apply as catalysts in theselective hydration of nitriles into amides in pure aqueous medium and neutralconditions [2].Ru(III) complexes serve as precursors to Ru(II) by a reduction in vivo bybiological reductants such as glutathione and ascorbic acid [3].*Ph.D., Ton Duc Thang University, HCM City Industry and Trade College;Email: buixuanvuong@tdt.edu.vn66TẠP CHÍ KHOA HỌC ĐHSP TPHCMBui Xuan Vuong_____________________________________________________________________________________________________________Among ruthenium complexes, ruthenium(II) complexes are still being the mostattracted for scientific researchers. They have indisputable advantages, for a wide rangeof applications such as optical power limiting [4-6], optical data processing, biologicalimaging [7], photosensitizers (PS) in the conversion of solar energy [8] and PS forapplication in photodynamic therapy (PDT) [9-11]. For example, ruthenium(II)complexes containing a benzimidazole ligand have important applications inoptoelectronic devices, efficient sensitizers for molecular photovoltaics [12]. A seriesof Ru(II) complexes of polyphosphine ligands has been used as catalyst precursors inthe homogeneous hydrogenation of cyclohexene, cyclohexanone, propanal and 2cyclohexen-1-one [13]. These polyphosphine Ru(II) complexes show enhancedcatalytic activities compared to monodentate, bidentate phosphine, arsine analog. Fromanother point of view, tetraamine-based ruthenium(III) and (II) complexes constitute isvery interesting class of compounds for medicinal chemistry studies because of theirwater solubility, stability in an aqueous medium, and low cytotoxicity [3]. Furthermore,ruthenium(II) complexes possess many interesting properties such as luminescentproperty, high stability with a large number of potential ligands [6], allowing their usein practical applications.In this study, we focused on novel Ru(II) complex (Fig. 1). This is heterolepticRu(II) complex involving three bidentate ligands: two ligands (abbreviate: L) playingan important role for linear and nonlinear optical properties and a third ligand such asan anchor (abbreviate: A) for connecting with the quantum dots. This report presentsabout synthesis and characterization of this novel Ru(II) complex.Figure 1. Molecular structure of novel Ru(II) complex67TẠP CHÍ KHOA HỌC ĐHSP TPHCMSố 12(90) năm 2016____________________________________________________________________________________________________________2.Materials and method2.1. MaterialsMain chemical reagents used such as: Javel water Lacroix; 1,10-phenanthrolinemonohydrate, Sigma-Aldrich, ≥ 99%; Potassium cyanide, Sigma-Aldrich, ≥ 96%; );Potassium hydroxide, Sigma-Aldrich, ≥ 90%; Bromohexane, Sigma-Aldrich, ≥ 98%;n-Butyllithium solution 2.5M in hexane, Sigma-Aldrich; Triisopropyl borate, SigmaAldrich, ≥ 98%; 2-bromofluorene, Sigma-Aldrich, 95%; RuCl2(DMSO)4, SigmaAldrich, 98%; 5-bromo-1,10-phenanthroline, Sigma-Aldrich, 99%.2.2. Synthesis2.2.1. Synthesis of the new anchorFrom 1,10-phenanthroline monohydrate (compound A), anchor D wassynthesized following the scheme 1.Scheme 1. Synthesis of the Phen-COOH ligandIn a 500 ml round bottom flask, adding to 125 ml of Javel water (NaClO andNaCl aqueous solution) and 60 ml of distilled water. Then, 1 g (5.05x10 -3 mol) of 1,10phenanthroline monohydrate (compound A) and 0.8 g of tetra-n-butylammoniumhydrogen sulfate (2.36x10-3 mol) were dissolved in 100 ml of chloroform. Controllingthe temperature ToC = 20 oC and the pH = 8.6 (by NaOH 6M and HCl solution 2M) for2 hours 40 minutes. The organic phase was separated. Washing this organic phase withdistilled water (3x100 ml), saturated sodium chloride (1x100 ml) to collect organicphase. Drying a small water inside organic p ...