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Luminescent Complexes of Europium (III) with 2-(Phenylethynyl)-1,10-phenanthroline: The Role of the Counterions.

ABSTRACT: New antenna ligand, 2-(phenylethynyl)-1,10-phenanthroline (PEP), and its luminescent Eu (III) complexes, Eu(PEP)₂Cl₃ and Eu(PEP)₂(NO₃)₃, are synthesized and characterized. The synthetic procedure applied is based on reacting of europium salts with ligand in hot acetonitrile solutions in molar ratio 1 to 2. The structure of the complexes is refined by X-ray diffraction based on the single crystals obtained. The compounds [Eu(PEP)₂Cl₃]·2CH₃CN and [Eu(PEP)₂(NO₃)₃]∙2CH₃CN crystalize in monoclinic space group P2_1/n and P2_1/c, respectively, with two acetonitrile solvent molecules. Intra- and inter-ligand π-π stacking interactions are present in solid stat and are realized between the phenanthroline moieties, as well as between the substituents and the phenanthroline units. The optical properties of the complexes are investigated in solid state, acetonitrile and dichloromethane solution. Both compounds exhibit bright red luminescence caused by the organic ligand acting as antenna for sensitization of Eu (III) emission. The newly designed complexes differ in counter ions in the inner coordination sphere, which allows exploring their influence on the stability, molecular and supramolecular structure, fluorescent properties and symmetry of the Eu (III) ion. In addition, molecular simulations are performed in order to explain the observed experimental behavior of the complexes. The discovered structure-properties relationships give insight on the role of the counter ions in the molecular design of new Eu (III) based luminescent materials.

SUBMITTER: Elenkova D

PROVIDER: S-EPMC8658859 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Europium (III) Organic Complexes in Porous Boron Nitride Microfibers: Efficient Hybrid Luminescent Material.

Project description:We report the design and synthesis of a novel kind of organic-inorganic hybrid material via the incorporation of europium (III) ?-diketonate complexes (Eu(TTA)3, TTA?=?2-thenoyltrifluoroacetone) into one-dimensional (1D) porous boron nitride (BN) microfibers. The developed Eu(TTA)3@BN hybrid composites with typical 1D fibrous morphology exhibit bright visible red-light emission on UV illumination. The confinement of Eu(TTA)3 within pores of BN microfibers not only decreases the aggregation-caused quenching in solid Eu(TTA)3, but also improves their thermal stabilities. Moreover, The strong interactions between Eu(TTA)3 and porous BN matrix result in an interesting energy transfer process from BN host to TTA ligand and TTA ligand to Eu3+ ions, leading to the remarkable increase of red emission. The synthetic approach should be a very promising strategy which can be easily expanded to other hybrid luminescent materials based on porous BN.

| S-EPMC5043355 | biostudies-literature

Bis(2,6-dihy-droxy-benzoato-?O,O)(nitrato-?O,O')bis-(1,10-phenanthroline-?N,N')europium(III).

Project description:The title mononuclear complex, [Eu(C(7)H(5)O(3))(2)(NO(3))(C(12)H(8)N(2))(2)], is isostructural with those of other lanthanides. The Eu atom is in a pseudo-bicapped square-anti-prismatic geometry, formed by four N atoms from two chelating 1,10-phenanthroline (phen) ligands and by six O atoms, four from two 2,6-dihy-droxy-benzoate (DHB) ligands and the other two from a nitrate anion. ?-? stacking inter-actions between phen and DHB ligands [centroid-centroid distances = 3.5312?(19) and 3.8347?(16)?Å], and between phen and phen ligands [face-to-face separation = 3.433?(4)?Å] of adjacent complexes stabilize the crystal structure. Intra-molecular O-H?O hydrogen bonds are observed in the DHB ligands.

| S-EPMC3011488 | biostudies-literature

Exceptional Oxygen Sensing Properties of New Blue Light-Excitable Highly Luminescent Europium(III) and Gadolinium(III) Complexes.

Project description:New europium(III) and gadolinium(III) complexes bearing 8-hydroxyphenalenone antenna combine efficient absorption in the blue part of the spectrum and strong emission in polymers at room temperature. The Eu(III) complexes show characteristic red luminescence whereas the Gd(III) dyes are strongly phosphorescent. The luminescence quantum yields are about 20% for the Eu(III) complexes and 50% for the Gd(III) dyes. In contrast to most state-of-the-art Eu(III) complexes the new dyes are quenched very efficiently by molecular oxygen. The luminescence decay times of the Gd(III) complexes exceed 1 ms which ensures exceptional sensitivity even in polymers of moderate oxygen permeability. These sensors are particularly suitable for trace oxygen sensing and may be good substitutes for Pd(II) porphyrins. The photophysical and sensing properties can be tuned by varying the nature of the fourth ligand. The narrow-band emission of the Eu(III) allows efficient elimination of the background light and autofluorescence and is also very attractive for use e.g. in multi-analyte sensors. The highly photostable indicators incorporated in nanoparticles are promising for imaging applications. Due to the straightforward preparation and low cost of starting materials the new dyes represent a promising alternative to the state-of-the-art oxygen indicators particularly for such applications as e.g. food packaging.

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Project description:The title complex, [Eu(2)(C(11)H(7)O(3))(6)(C(12)H(8)N(2))(2)]·2H(2)O, has a centrosymmetric binuclear cage structure in which the two Eu(III) ions are both nine-coordinated and bridged by 6-hy-droxy-1-naphthoate (L) ligands, with an Eu? Eu separation of 4.1594?(4)?Å. The remaining coordination sites are occupied by two N atoms from one 1,10-phenanthroline (phen) and two O atoms from an L ligand. The six 6-hydr-oxy-1-naphthoate groups coordinate each Eu(III) atom in three different ways, namely ?(2)-?(1):?(1)-bridging, ?(1)-?(1):?(1)-chelating, and ?(2)-?(1):?(2)-chelating/bridging modes. Adjacent discrete dinuclear units are linked into a two-dimensional sheet parallel to (011) by inter-molecular O-H?O hydrogen-bonding inter-actions. The sheets are cross-linked by water mol-ecules, forming a three-dimensional network. In addition, ?-? stacking inter-actions, with a centroid-centroid separation of 3.547?(2)?Å are observed.

| S-EPMC2972167 | biostudies-literature

Tris(N-benzyl-N-methyl-dithio-carbamato-?S,S')(1,10-phenanthroline-?N,N')europium(III).

Project description:In the title compound, [Eu(C(9)H(10)NS(2))(3)(C(12)H(8)N(2))], the Eu(III) atom exists in a distorted square-anti-prismatic coordination geometry. Both dithio-carbamate and the N-heterocyclic ligands function in a chelating mode.

| S-EPMC2971428 | biostudies-other

cis-Dichloridobis(1,10-phenanthroline)chromium(III) chloride.

Project description:In the title complex, [CrCl(2)(C(12)H(8)N(2))(2)]Cl, the Cr(III) ion is situated on a twofold rotation axis and displays a slightly distorted octa-hedral CrCl(2)N(4) coordination geometry. The Cr environment is composed of a cis arrangement of two 1,10-phenanthroline and two chloride ligands. The chloride counter-anion exhibits half-occupation and is equally disordered over two positions.

| S-EPMC3051699 | biostudies-literature

Tetra-?-acetato-?O:O';?O,O':O';?O:O,O'-bis-[(acetato-?O,O')(1,10-phenanthroline-?N,N')europium(III)].

Project description:In the title centrosymmetric dinuclear Eu(III) complex, [Eu(2)(CH(3)COO)(6)(C(12)H(8)N(2))(2)], each Eu(III) cation is coordinated by seven O atoms from five acetate anions and two N atoms from one phenanthroline ligand in a distorted tricapped trigonal-prismatic geometry. Four acetate anions bridge two Eu(III) cations to form the dinuclear complex, with an Eu?Eu distance of 3.9409?(8)?Å. Weak inter-molecular C-H?O hydrogen bonding is present in the crystal structure.

| S-EPMC2979550 | biostudies-literature

Tetra-?-acetato-?O:O';?O,O':O;?O:O,O'-bis-[(acetato-?O,O')(1,10-phenanthroline-?N,N')europium(III)].

Project description:In the title centrosymmetric dinuclear complex, [Eu(2)(CH(3)CO(2))(6)(C(12)H(8)N(2))(2)], the Eu(III) atom is nine-coordinated by two N atoms from a 1,10-phenanthroline ligand and seven O atoms from five acetate ligands (two bidentate, three monodentate). The crystal structure is stabilized by ?-? stacking inter-actions between the pyridine and benzene rings of adjacent mol-ecules, with a centroid-centroid distance of 3.829?(2)?Å.

| S-EPMC3011772 | biostudies-literature

Tetrakis[?-3-(3-pyridyl)acrylato-?O:O']bis{(1,10-phenanthroline-?N,N')[3-(3-pyridyl)acrylato-?O,O']europium(III)} pentahydrate.

Project description:The europium(III) ion in the title compound, [Eu(2)(C(8)H(6)NO(2))(6)(C(12)H(8)N(2))(2)]·5H(2)O, is coordinated by seven carboxyl-ate O atoms and two N atoms from one phenanthroline mol-ecule. The carboxyl-ate groups of 3-(3-pyrid-yl)acrylate link pairs of europium(III) ions, forming centrosymmetric dinuclear units, which further assemble into a sheet parallel to the (001) plane through hydrogen-bonding inter-actions involving the uncoordinated water mol-ecules. One water molecule is disordered.

| S-EPMC2915131 | biostudies-literature

cis-Difluoridobis(1,10-phenanthroline)chromium(III) perchlorate monohydrate.

Project description:The title complex, [CrF(2)(C(12)H(8)N(2))(2)]ClO(4)·H(2)O, displays a slightly distorted octa-hedral coordination geometry around the central chromium(III) ion. The Cr environment is composed of a cis arrangement of two 1,10-phenanthroline [average Cr(III)-N = 2.0726 (10) Å] and two fluoride [average Cr(III)-F = 1.8533 (6) Å] ligands. The water molecule forms a hydrogen bond to fluorine in a neighbouring cation.

| S-EPMC2960161 | biostudies-literature

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