Synthesis and Characterization of a Heteroleptic Ru(II) Complex of Phenanthroline Containing Oligo-Anthracenyl Carboxylic Acid Moieties

Abstract

In an effort to develop new ruthenium(II) complexes, this work describes the design, synthesis and characterization of a ruthenium(II) functionalized phenanthroline complex with extended π-conjugation. The ligand were L1 (4,7-bis(2,3-dimethylacrylic acid)-1,10-phenanthroline), synthesized by a direct aromatic substitution reaction, and L2 (4,7-bis(trianthracenyl-2,3-dimethylacrylic acid)-1,10-phenanthroline), which was synthesized by the dehalogenation of halogenated aromatic compounds using a zero-valent palladium cross-catalyzed reaction in the absence of magnesium-diene complexes and/or cyclooctadienyl nickel (0) catalysts to generate a new carbon-carbon bond (C-C bond) polymerized hydrocarbon units. The ruthenium complex [RuL1L2(NCS)2] showed improved photophysical properties (red-shifted metal-to-ligand charge-transfer transition absorptions and enhanced molar extinction coefficients), luminescence and interesting electrochemical properties. Cyclic and square wave voltammetry revealed five major redox processes. The number of electron(s) transferred by the ruthenium complex was determined by chronocoulometry in each case. The results show that processes I, II and III are multi-electron transfer reactions while processes IV and V involved one-electron transfer reaction. The photophysical property of the complex makes it a promising candidate in the design of chemosensors and photosensitizers, while its redox-active nature makes the complex a potential mediator of electron transfer in photochemical processes.

A High Molar Extinction Coefficient Ru(II) Complex Functionalized withcis-Dithiocyanato-bis-(9-anthracenyl-10-(2-methyl-2-butenoic acid)-1,10-phenanthroline): Potential Sensitizer for Stable Dye-Sensitized Solar Cells

“…As envisaged, enhanced spectral response was found for complex containing anthracenyl functionality as compared to that without anthracene. However, of particular relevance in the context of this report in relation to our previous studies and reports on the increasing number of anthracene functionality in a particular ruthenium polypyridyl complex in which molar extinction coefficient values are reduced due to molecular aggregation [38][39][40]. On the basis of this, we set out to investigate and discuss the photophysical and electrochemical properties of a new-type monoanthracenyl functionalized phenanthroline heteroleptic ruthenium(II) complex in relation to its potential use as a photosensitizer for application in the dye-sensitized solar cells (DSSCs) and other optoelectronic devices.…”

Treatment of Leishmania (Leishmania) Amazonensis-Infected Mice with a Combination of a Palladacycle Complex and Heat-Killed Propionibacterium acnes Triggers Protective Cellular Immune Responses

“…The evidence that antitumor drugs may also display antileishmanial activity has also stimulated the screening of these compounds in vitro and in clinical trials (Fuertes et al, 2008; Sanderson et al, 2014). Palladacycle complexes have been pointed out as a new class of antitumoral and antimicrobial agents (Caires, 2007; Elgazwy et al, 2012) and the leishmanicidal and tripanocidal effect of some of these compounds has also been demonstrated (Fricker et al, 2008; Navarro et al, 2008; Matsuo et al, 2010). More recently the activity of the palladacycle complex DPPE 1.2 on L. (L.) amazonensis was described (Paladi et al, 2012).…”

Synthesis, Characterization, Electrochemistry, and Spectroscopic Properties of Some Anthracenyl Functionalized Phthalocyanine Complexes of Ruthenium(II)

“…All chemical and reagents were analytically pure and used without further purification. 9-Anthracenyl-10-(2,3-dimethylacrylic acid) and 9-dianthracenyl-10-(2,3dimethylacrylic acid) were synthesized as described in the literature [14]. The ruthenium(II) phthalocyanine complexes were synthesized as reported in the literature with slight modifications [16].…”

“…In the present work, however, we focused our attention on the incorporation of ruthenium as the metal center into the cavity of nonperipheral substituted phthalocyanines using RuCl 2 (DMSO) 4 as metal precursor [12] and functionalized anthracene [13][14][15] derivatives as substituents and, most importantly, on developing an efficient, direct synthesis for these compounds. A direct substitution method may be useful in the syntheses of Pc most importantly where substituents are not stable in the condensation of precursor or the condensation is not qualitative [16].…”

“…The emission is likely to originate from an excited state of 3 MLCT (d (Ru) → * ) macrocycle and anthracene characters. An extended system in the complexes has allowed a greater delocalization of the excited electron, which reduces the adjustments in local bond displacements and modulates the vibrational overlap between states[14,29,30].3.4. NMR Spectra.The 1 H NMR spectra for (C 1 R RuPc) and (C 3 R RuPc)(Figures 3 and 4)show the expected aggregation and broadening of the signals.…”