Tuning the Luminescent Properties of Ruthenium(II) Amino‐1,10‐Phenanthroline Complexes by Varying the Position of the Amino Group on the Heterocycle

Abel, Anton S.; Zenkov, I. S.; Averin, Alexei D.; Cheprakov, Andrei V.; Bessmertnykh‐Lemeune, Alla; Orlinson, B. S.; Beletskaya, I. P.

doi:10.1002/cplu.201900206

Cited by 10 publications

(7 citation statements)

References 64 publications

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“…The only reported examples of such chelators are the complexes containing mixed-donor (N, O, S) macrocycles (i.e., crown-ether-type receptors fused at the central six-membered ring via positions 5 and 6 or attached at positions 4 and 7 of the heterocycle, or azacrown-type derivatives bearing two macrocycles attached at positions 4 and 7 of the phenanthroline ring) [21,22]. On the other hand, the emissive properties of ruthenium(II) tris(diimine) complexes with aminophenanthroline ligands are strongly dependent on the position of the amino-substituent attached to the heterocycle, and emission quantum yields of complexes involving 4-substituted phen ligands are expected to be low [23,24]. This could be detrimental for the sensibility of chemosensors.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, the introduction of the amino substituents in the 3-or 5-position of the 1,10-phenanthroline ring results only in a small decrease in luminescence quantum yields compared to that of the parent complex [Ru(bpy)2(phen)](PF6)2, while the brightness of the complexes with the 3substituted ligands is comparable to that of the parent complex. In these Ru 2+ complexes, the signaling and receptor units are directly connected, and HOMO is localized on the aminophenanthroline ligand [24]. As a consequence, analyte binding by the nitrogen atom of the substituent should strongly affect the HOMO energy, leading presumably to significant modulation of the absorption and emission properties.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium(II) Complexes with (3-Polyamino)phenanthrolines: Synthesis and Application in Sensing of Cu(II) Ions

et al. 2022

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This work deals with the development of water-soluble optical sensors based on ruthenium(II) tris(diimine) complexes that exhibit high molar absorptivity and are emissive in aqueous media. Palladium-catalyzed arylation of polyamines with 3-bromo-1,10-phenanthroline (Brphen) and [Ru(bpy)2(Brphen)](PF6)2 (bpy = 2,2’-bipyridine) was explored to prepare Ru2+ complexes with 1,10-phenanthrolines (phen) substituted by linear polyamines (PAs) at position 3 of the heterocycle ([Ru(bpy)2(phen⎼PA)](PF6)2). The most convenient synthetic pathway leading to the target molecular probes includes the preparation of phen⎼PA ligands, followed by ruthenium complexation using cis-Ru(bpy)2Cl2. Complexes bearing a polyamine chain directly linked to phenanthroline core are emissive in aqueous media and their quantum yields are comparable to that of parent [Ru(bpy)3](PF6)2. Their structure can be easily adapted for detection of various analytes by modification of amine groups. As an example, we prepared the emissive complex Ru(N2P2phen) which is suitable for the dual channel (spectrophotometry and luminescence (ON–OFF probe)) selective detection of Cu2+ ions at the physiological pH levels with limits of detection (LOD) by spectrophotometry and fluorescence spectroscopy equal to 9 and 6 μM, respectively, that is lower than the action level in drinking water for copper as prescribed by the US Environmental Protection Agency.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ruthenium(II) Complexes with (3-Polyamino)phenanthrolines: Synthesis and Application in Sensing of Cu(II) Ions

et al. 2022

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“…In the case of Ru(Phen-3NPy 2 ) and Ru(Phen-3NPy 2 )Pd complexes one may observe also a band in 340-370 nm region (Figure 5a). It is characteristic for Ru complexes of 3aminosubstituted 1,10-phenanthrolines 36,52,53 and probably corresponds to an interligand bpy/phen-based LLCT transition 54 . To note, coordination of palladium with dpa moiety in Ru(Phen-3NPy 2 ) leads to a hypsochromic shift of this band from 369 to 343 nm.…”

Section: Absorption and Emission Propertiesmentioning

confidence: 98%

“…Variation of the structure of the bridging ligand allows fine tuning the catalytic system in view of enhancing its activity 15,34 . The nature of substituents in the heterocyclic ligand and their position in the core significantly influence spectral, electrochemical and catalytic properties of Ru complexes [35][36][37][38][39] . One may assume that binding metal complex and photocatalyst via various positions of the heterocyclic ligand (1,10-phenanthroline or 2,2'-bipyridine) will help to improve https://doi.org/10.26434/chemrxiv-2024-jcjgd ORCID: https://orcid.org/0000-0002-2951-4529 Content not peer-reviewed by ChemRxiv.…”

Section: Introductionmentioning

confidence: 99%

Ru(II)–Pd(II) dinuclear complexes of di(pyridin-2-yl)amino-substituted 1,10-phenanthrolines: synthesis, characterization and application for catalysis

Ionova,

Dmitrieva,

Abel

et al. 2024

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Dinuclear complexes bearing Ru(II) photoactive center are of interest for the development of efficient dual catalysts for many photocatalyzed reactions. Ditopic polypyrine ligands – bis(pyridine-2-yl)amino-1,10-phenanthrolines – containing additional coordination site (bis(pyridine-2-yl)amine, dpa) at positions 3, 4 or 5 of 1,10-phenanthroline core (Phen-3NPy2, Phen-4NPy2 and Phen-5NPy2) were synthesized. They were used as bridging ligands to obtain dinuclear complexes of composition [(bpy)2Ru(Phen-NPy2)PdCl2](PF6)2 (Ru(Phen-NPy2)Pd) via stepvise comlexing in good yields. Ru(II) is coordinated to 1,10-phenanthroline in these complexes, while Pd(II) is bound to dpa chelating moiety, which was established by NMR spectroscopy and X-ray single crystal analysis. The influence of the position of dpa in phenanthroline ring on the structural, optical and electrochemical properties of Ru(Phen-NPy2)Pd complexes was studied. The complexes possess photoluminescence in argon-saturated MeCN solution with maxima in the range of 615–625 nm, emission quantum yields range from 0.11 to 0.15 for Ru(Phen-NPy2) complexes and from 0.018 to 0.026 for dinucear Ru(Phen-NPy2)Pd complexes. All the complexes have high extinction coefficients in the range of 370–470 nm, efficiently absorb visible light and can be used as photocatalysts. The Ru2+/3+ potential in Ru(Phen-NPy2)Pd complexes showed no significant dependence on dpa position, while Pd2+/0 reduction potential was quite lower for Ru(Phen-3NPy2)Pd and Ru(Phen-NPy2)Pd, than for Ru(Phen-NPy2)Pd (–0.57V and –0.72V vs Ag/AgCl, KCl(sat), respectively). The behaviour of the complexes was studied in Сu-free Sonogashira coupling under blue LED (12 W) irradiation. The reaction proceeds three times faster when Ru(Phen-4NPy2)Pd and Ru(Phen-3NPy2)Pd are used as catalysts precursors than in the case of mixed catalytic system Ru(bpy)3(PF6)2/(RNPy2)PdCl2.

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“…It is rational to use the Pd-catalyzed amination at the second step as it is depicted on Scheme 1. Earlier we demonstrated Pd-catalyzed diamination to be useful in one-step syntheses of symmetrical adamantane-containing diamino derivatives of pyridines [32], quinolines [33], and 1,10-phenanthrolines [34]. Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines

et al. 2021

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N-heteroaryl substituted adamantane-containing amines are of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of N-heterocycles has been substituted by the amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy. The introduction of the second amino substituent in 4-amino-6-chloropyrimidine, 2-amino-chloropyrazine, and 1-amino-3-chloroisoquinoline was achieved using Pd(0) catalysis.

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Tuning the Luminescent Properties of Ruthenium(II) Amino‐1,10‐Phenanthroline Complexes by Varying the Position of the Amino Group on the Heterocycle

Cited by 10 publications

References 64 publications

Ruthenium(II) Complexes with (3-Polyamino)phenanthrolines: Synthesis and Application in Sensing of Cu(II) Ions

Ruthenium(II) Complexes with (3-Polyamino)phenanthrolines: Synthesis and Application in Sensing of Cu(II) Ions

Ru(II)–Pd(II) dinuclear complexes of di(pyridin-2-yl)amino-substituted 1,10-phenanthrolines: synthesis, characterization and application for catalysis

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines

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