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Nanoscale ; 2020 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-32108842


The development of new contactless thermal nanosensors based on a ratiometric approach is of significant interest. To overcome the intrinsic limitations of thermally coupled levels, a dual activation strategy was applied. Dual activation was performed using co-doped single nanoparticles and a binary mixture of single-doped nanoparticles. Co-doped and mixed YVO4:Nd3+/Eu3+ nanoparticles were successfully demonstrated as luminescent nanothermometers and their thermometric performance, in terms of thermal sensitivity, temperature resolution and repeatability, was studied and compared.

Dalton Trans ; 2020 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-32083636


A series of Cu(i) halide complexes derived from tris(2-pyridyl)phosphine (Py3P), [Cu2(Py3P)2X2] (X = Cl, Br, I), have been synthesized by a straightforward reaction in solution or through a mechanochemical route. At room temperature, the solid complexes exhibit bright dual-mode photoluminescence (λmax = 520-550 nm, τ = 14.5-20.0 µs, and ΦPL ≈ 53%), expressed by thermally activated delayed fluorescence (TADF) combined with phosphorescence (PH), originating from 1(M + X)LCT and 3(M + X)LCT excited states, respectively. Remarkably, the balance of these radiative processes at 300 K is regulated by halogen atom nature, switching from TADF-assisted phosphorescence to PH-admixed TADF. The emission of [Cu2(Py3P)2Cl2] at 300 K is largely contributed by PH (73%) admixed with the TADF fraction (27%) and [Cu2(Py3P)2Br2] also emits mainly PH (65%) admixed with the larger TADF fraction (35%). Meanwhile, for [Cu2(Py3P)2I2], the TADF channel becomes dominating (61%) and PH contribution drops to 39%. The photophysical study corroborated by (TD)DFT computations has revealed that this effect arises mainly from the narrowing of the ΔE(S1 - T1) gap of the [Cu2(Py3P)2X2] complexes in the order Cl (1500 cm-1) > Br (1250 cm-1) > I (1000 cm-1) which facilitates the TADF pathway and suppresses PH in the same order.

Inorg Chem ; 59(1): 244-253, 2020 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-31814406


A flexible bidentate cyclic phosphine, namely, 1,5-bis(p-tolyl)-3,7-bis(pyridin-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP), was used as a template to construct a family of binuclear heteroleptic phosphine alkynyl complexes [PNNP(AuC2R)2], with R = Ph, C6H10OH, C5H8OH, (CH3)2COH, Ph2COH. All complexes obtained were characterized by CHN elemental analysis, NMR spectroscopy, and single-crystal X-ray analysis. It was found that the gold(I) complexes demonstrate a different organization of the crystal structure depending on the nature of the cocrystallized solvent (dichloromethane, acetone, and acetonitrile) because of formation of the supramolecular complexes through hydrogen bonding. These weak interactions appear to determine the conformation, packing, and spatial cooperation of flexible complex molecules that are reflected in the photophysical properties, which were carefully investigated in solution and in the solid state. The complexes demonstrate weak emission in solution at room temperature, and freezing results in blue shifting of the emission, which is accompanied by a significant increase in the luminescence intensity. Being isolated from dichloromethane, all gold(I) complexes exhibit green phosphorescence in the solid state, and the complexes with R = Ph and Ph2COH display substantial variation of their emission color after recrystallization from acetone and acetonitrile, respectively, which manifests itself as a significant bathochromic shift of up to 120 nm. The structural nonrigidity of the gold(I) complexes obtained and its impact on the properties of low-energy excited states were investigated in detail by density functional theory calculations, which indicate the significant role of the structural flexibility of the PNNP ligand in the formation of the low-energy excited states and confirm the impact of rotation of the functional groups in the coordination sphere on the emission properties of complexes.

Data Brief ; 27: 104605, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31667318


In this data article, we present the single-crystal XRD data of phenanthrene-9,10-dicarbonitriles. Detailed structure analysis and photophysical properties were discussed in our previous study, "Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies" (Afanasenko et al., 2020). The data include the intra- and intermolecular bond lengths and angles.

Inorg Chem ; 58(12): 7698-7704, 2019 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-31144500


A series of novel charged disilver(I) complexes with pyridyl-containing phospholanes was synthesized. These complexes were characterized using a range of spectroscopic techniques and single-crystal and powder X-ray diffraction. The complexes demonstrate solid-state near-infrared (NIR) luminescence (765-902 nm) that is unique for dinuclear AgI complexes. Combined spectroscopic/quantum chemical analysis suggests that the NIR luminescence of complexes 4-6 in the solid state is mainly due to crystal packing effects.

Inorg Chem ; 58(2): 1048-1057, 2019 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-30601648


The unique L2Cu6I6 complexes containing two Cu3I3 units have been obtained via reaction of 1,5-diaza-3,7-diphosphacyclooctanes bearing ethylpyridyl substituents at phosphorus atoms with an excess of copper iodide. The structure of one of the complexes was confirmed by X-ray diffraction. It was shown that the complexes can exist in two crystalline phases with different parameters of the unit cell, which were detected by the PXRD data analyses. The solvent-free crystalline phases of the complexes display rare solid-state white emission at room temperature, which is observed due to the presence of two broad bands in the emission spectra with maxima at 464 and 610 nm. Quantum chemical computations show that the high-energy band has 3(M+X)LCT origin, whereas the low-energy band is interpreted as 3CC. The quantum yields of white luminescence of complexes reach 15-20%.