Ytterbium 10-carboxyperylene-3,4,9-tricarboxylates for targeted NIR luminescent bioimaging.

Two new ytterbium coordination compounds Yb(HPTC)(HO) (Yb1) and Yb(HPTC)(Phen) (Yb2) were obtained using 10-carboxyperylene-3,4,9-tricarboxylate ion (HPTC) as a sensitizer. Both coordination compounds exhibited intense NIR-II luminescence upon excitation in the visible range and formed stable suspensions with nanoparticles of 50-70 nm in size in an aqueous solution of sodium alginate. Both complexes demonstrated non-toxicity up to at least 25 mg L in two cell cultures: cancer cells MCF7 and embryonic cells HEK293T - making them suitable for bioimaging.

Controlled Reduction of Sn in the Complex Iodide CsSnI with Metallic Gallium.

Metal gallium as a low-melting solid was applied in a mixture with elemental iodine to substitute tin(IV) in a promising light-harvesting phase of CsSnI by a reactive sintering method. The reducing power of gallium was applied to influence the optoelectronic properties of the CsSnI phase via partial reduction of tin(IV) and, very likely, substitute partially Sn by Ga. The reduction of Sn to Sn in the CsSnI phase contributes to the switching from -type conductivity to n-type, thereby improving the total concentration and mobility of negative-charge carriers.

NIR luminescence thermometers based on Yb-Nd coordination compounds for the 83-393 K temperature range.

Multimetallic neodymium-ytterbium-gadolinium compounds with 9-anthracenate and 9-acridinate anions were tested in order to create the first luminescent thermometer for elevated temperatures. High luminescence intensity and high signal resolution were reached thanks to the concentration quenching elimination due to the partial substitution of the emitting ions with Gd. As a result, NIR emitting materials for luminescence thermometry in the wide temperature range (83-393 K) based on lanthanide coordination compounds (CCs) were obtained.

Dual vis-NIR emissive bimetallic naphthoates of Eu-Yb-Gd: a new approach toward Yb luminescence intensity increase through Eu → Yb energy transfer.

Homo- and heteroligand mono-, bi-, and trimetallic lanthanide naphtoates EuYbGd(naph)(Phen) (n = 0, 1) were obtained and thoroughly investigated. Homoligand naphthoates of the new phase were obtained as anhydrous powders from water. The photophysical properties of the obtained compounds were studied in detail.

Highly NIR-emitting ytterbium complexes containing 2-(tosylaminobenzylidene)-N-benzoylhydrazone anions: structure in solution and use for bioimaging.

Solution behaviour in DMSO using 1D and 2D NMR spectroscopy was performed for lanthanide complexes Ln(L)(HL) and Ln(HL)Cl, containing non-macrocyclic 2-(tosylamino)-benzylidene-N-benzoylhydrazone (HL), and the structure of [Yb(L)] cation in solution was determined. Based on the NMR data, the possibility to obtain novel complexes containing [Ln(L)] was predicted, which was successfully synthesized, and the crystal structure of K(CHOH)[Yb(L)] was determined. Thanks to its high quantum yield of NIR luminescence (1.

New approach to increase the sensitivity of Tb-Eu-based luminescent thermometer.

The formation of trimetallic terbium-europium-gadolinium complexes was proposed as an approach to increase the sensitivity of the corresponding terbium-europium complexes for temperature measurement due to the suppression of multiphotonic emission. This approach results in over a 2-fold increase of the sensitivity of Eu-Tb carboxylate, which reached 5.3% K-1 in the physiological range.

Indium Doping of Lead-Free Perovskite CsSnI.

Structure and properties of an inorganic perovskite CsSnI demonstrated its potential as a light-harvester or electron-hole transport material; however, its optoelectronic properties are poorer than those of lead-based perovskites. Here, we report the way of light tuning of absorption and transport properties of cesium iodostannate(IV) CsSnI via partial heterovalent substitution of tin for indium. Light absorption and optical bandgaps of materials have been investigated by UV-vis absorption and photoluminescent spectroscopies.

On the development of a new approach to the design of lanthanide-based materials for solution-processed OLEDs.

The targeted design of lanthanide-based emitters for solution-processed organic light-emitting diodes (OLEDs) resulted in obtaining an NIR OLED with one of the highest efficiencies among ytterbium-based solution-processed OLEDs (30 μW W-1). The design was aimed at the combination of high luminescence efficiency with solubility and charge carrier mobility. The latter was achieved thanks to the introduction of the purposefully selected neutral ligands, which combine electron mobility and the ability to sensitize lanthanide luminescence.

From Isolated Anions to Polymer Structures through Linking with I: Synthesis, Structure, and Properties of Two Complex Bismuth(III) Iodine Iodides.

We report the synthesis, crystal structures, and optical properties of two new compounds, KBiI(I)·14HO (1) and (NH)BiI(I)·4.5HO (2), as well as the electronic structure of the latter. They crystallize in tetragonal space group P4/ mmm with the unit cell parameters a = 12.

The peculiarities of complex formation and energy transfer processes in lanthanide complexes with 2-(tosylamino)-benzylidene-N-benzoylhydrazone.

Depending on the local excess of lanthanide ions (Ln = Lu, Yb, Er, Dy, Tb, Gd, Eu, Nd) or 2-(tosylamino)-benzylidene-N-benzoylhydrazone (H2L), lanthanide complexes, containing either a mono-deprotonated ligand (Ln(HL)2X, X = Cl, NO3) or both mono- and dideprotonated ligands (Ln(L)(HL)), were preparatively obtained. The crystal structures of Lu(HL)2Cl, Yb(L)(HL)(H2O)2, Yb(L)(HL)(EtOH)2(H2O) and Er(L)(HL), determined by single crystal diffraction data or from powder diffraction data using Rietveld refinement, have shown the surprising resemblance. The study of luminescence temperature dependence of Eu(HL)2Cl and Eu(L)(HL) showed that europium luminescence is quenched by thermally-activated 5D0 → T1 energy transfer.

Deciphering three beneficial effects of 2,2'-bipyridine-N,N'-dioxide on the luminescence sensitization of lanthanide(III) hexafluoroacetylacetonate ternary complexes.

Lanthanide hexafluoroacetylacetonate ternary complexes with 2,2'-bipyridine-N,N'-dioxide, [Ln(hfa)(3)(bpyO2)], were synthesized for Ln = Eu, Gd, Tb, and Lu and fully characterized by elemental, thermal, and mass-spectrometric analyses. The X-ray crystal structure of [Eu(hfa)(3)(bpyO2)]·0.5C(6)H(6) reveals an octa-coordinate metal ion lying in a severely distorted trigonal dodecahedron geometry; the Eu-O distances lie in the range 2.

Highly luminescent and triboluminescent coordination polymers assembled from lanthanide β-diketonates and aromatic bidentate O-donor ligands.

The reaction of hydrated lanthanide hexafluoroacetylacetonates, [Ln(hfa)(3)(H(2)O)(2)], with 1,4-disubstituted benzenes afforded a new series of one-dimensional coordination polymers [Ln(hfa)(3)(Q)](∞), where Ln = Eu, Gd, Tb, and Lu and Q = 1,4-diacetylbenzene (acbz), 1,4-diacetoxybenzene (acetbz), or 1,4-dimethyltherephtalate (dmtph). X-ray single crystal analyses reveal [Ln(hfa)(3)(acbz)](∞) (Ln = Eu, Gd, Tb) consisting of zigzag polymeric chains with Ln-Ln-Ln angles equal to 128°, while the arrays are more linear in [Eu(hfa)(3)(acetbz)](∞) and [Eu(hfa)(3)(dmtph)](∞), with Ln-Ln-Ln angles of 165° and 180°, respectively. In all structures, Ln(III) ions are 8-coordinate and lie in distorted square-antiprismatic environments.

Theoretical study of structure and electronic absorption spectra of some Schiff bases and their zinc complexes.

Tetradentate Schiff bases (H(2)L(i)), derivatives of salicylic aldehyde (H(2)L(1), H(2)L(2)) or o-vanillin (H(2)L(3), H(2)L(4)) with ethylenediamine or o-phenylenediamine as a bridge, and their zinc complexes were studied experimentally and theoretically in view of their possible application as emitters in organic light emitting diodes (OLEDs). The composition of thin films of the complexes was analyzed using a combination of different experimental and molecular modeling techniques taking into account changes in the Gibbs free energy of dehydration and dimerization reactions. The absorption spectra of the initial Schiff bases were investigated in methanol solutions, while the absorption spectra of their zinc complexes were investigated in thin films.

Role of the ancillary ligand N,N-dimethylaminoethanol in the sensitization of Eu(III) and Tb(III) luminescence in dimeric beta-diketonates.

Two types of dimeric complexes [Ln2(hfa)6(mu2-O(CH2)2NHMe2)2] and [Ln(thd)2(mu2,eta2-O(CH2)2NMe2)]2 (Ln = YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- = hexafluoroacetylacetonato, thd- = dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the beta-diketonate.