Photoluminescence blinking in individual semiconducting and perovskite quantum dots reflects reduced emission quantum yield and represents an obstacle towards quantum dot applications. One of the origins of blinking is the presence of surface structural defects that can function as charge traps. To reduce the defects the surface can be modified by, , covering with ligands that are more strongly bound to the surface.
View Article and Find Full Text PDFLuminescent lanthanide complexes containing effective photosensitizers are promising materials for use in displays and sensors. The photosensitizer design strategy has been studied for developing the lanthanide-based luminophores. Herein, we demonstrate a photosensitizer design using dinuclear luminescent lanthanide complex, which exhibits thermally-assisted photosensitized emission.
View Article and Find Full Text PDFWe report the preparation and nanoscale photophysical characterization of mixed cation perovskite films of the composition MAFAPbI, with = 0, 0.3 and 0.5.
View Article and Find Full Text PDFConjugated polymer chains in compact conformations or in films exhibit spectral features that can be attributed to interactions between individual conjugated segments of the chain, including formation of aggregates or excimers. Here, we use atomic force microscopy (AFM) on single chains of the conjugated polymer polyfluorene (PFO) to control the intersegment interactions by mechanically unfolding the chain. Simultaneously with the force spectroscopy we monitor fluorescence from the single PFO chains using a fluorescence microscope.
View Article and Find Full Text PDFPolyfluorene-based copolymers such as poly(9,9-dioctylfluorene)-alt-5% [bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine] (F8-5% BSP) are efficient blue-emitting polymers with various electronic phases: F8 blue-emitting glassy phase, F8 ordered more red-emitting β-phase, and F8/BSP charge transfer (CT) state. Polymer light-emitting device performance and color purity can be significantly improved by forming β-phase segments. However, the role of the β-phase on energy transfer (ET) among glassy F8, β-phase, and F8/BSP CT state is unclear.
View Article and Find Full Text PDFSingle-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled real-time nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short- and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state.
View Article and Find Full Text PDFA combination of conductive atomic force microscopy (AFM) and confocal fluorescence microscopy was used to measure photocurrents passing through single trimeric photosytem I (PSI) complexes located in the vicinity of single gold nanorods (AuNRs). Simultaneous excitation of PSI and of the AuNR longitudinal plasmon mode and detection of photocurrents from individual PSI in relation to the position of single AuNRs enable insight into plasmon-induced phenomena that are otherwise inaccessible in ensemble experiments. We have observed photocurrent enhancement by the localized plasmons by a factor of 2.
View Article and Find Full Text PDFPoly(9,9-dioctylfluorene) (PFO) is one of the most important conjugated polymer materials, exhibiting outstanding photophysical and electrical properties. PFO is also known for a diversity of morphological phases determined by conformational states of the main chain. Our goal in this work is to address some of the key questions on formation and dynamics of one such conformation, the β-phase, by following in real time the evolution of fluorescence spectra of single PFO chains.
View Article and Find Full Text PDFPhys Chem Chem Phys
February 2020
Trivalent lanthanide complexes are an important class of luminescent material characterized by their strong absorption of light by the organic ligands and subsequent energy transfer to the lanthanide ion, realizing intense luminescence from the ion. With this mechanism of luminescence, the total quantum yield of a lanthanide complex is the product of the energy transfer efficiency from the ligand to the lanthanide ion and the "intrinsic" quantum yield of the lanthanide ion itself. The "absolute" method in measuring the quantum yield uses an integrating sphere, and this method can be used for measuring both the total and the intrinsic quantum yields.
View Article and Find Full Text PDFQuadrupolar interactions of porphyrin bearing two pentafluorophenylethynyl terminals (1) drove the formation of a successive one-dimensional staircase structure, i.e., J-aggregates, to yield millimeter-length needles with a single-crystalline character in methylcyclohexane solution.
View Article and Find Full Text PDFExpanded π-systems with a narrow highest occupied molecular orbital-lowest unoccupied molecular orbital band gap encounter deactivation of excitons due to the "energy gap law" and undesired aggregation. This dilemma generally thwarts the near-infrared (NIR) luminescence of organic π-systems. A sophisticated cofacially stacked π-system is known to involve exponentially tailed disorder, which displays exceptionally red-shifted fluorescence even as only a marginal emission component.
View Article and Find Full Text PDFUpon mechanical stimulation, 9-anthryl gold(I) isocyanide complex 3 exhibited a bathochromic shift of its emission color from the visible to the infrared (IR) region, which is unprecedented in its magnitude. Prior to exposure to the mechanical stimulus, the polymorphs 3α and 3β exhibit emission wavelength maxima (λ) at 448 and 710 nm, respectively. Upon grinding, the λ of 3α and 3β are bathochromically shifted to 900 nm, i.
View Article and Find Full Text PDFWe synthesized two new porous coordination polymers (PCPs) {Ln(OH)[Ru(dcbpy)]·4nHO} (Ln-Ru; Ln = Ce, Nd) composed of the luminescent ruthenium(II) metalloligand [Ru(4,4'-dcbpy)] ([4Ru]; 4,4'-dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and lanthanide ions Ln (Ln = Ce, Nd). These two PCPs Ln-Ru are isomorphous with the previously reported PCP La-Ru, and the lattice constants (a, c, and unit cell volume V) changed systematically according to the lanthanide contraction. All three Ln-Ru compounds have OH anion containing porous structures and a large number of hydrate water molecules within the pores, resulting in moderate ion conductivities (10-10 S cm) at 90% relative humidity (RH) and 298 K.
View Article and Find Full Text PDFLanthanide (Ln(III)) complexes form an important class of highly efficient luminescent materials showing characteristic line emission after efficient light absorption by the surrounding ligands. The efficiency is however lowered by back energy transfer from Ln(III) ion to the ligands, especially at higher temperatures. Here we report a new strategy to reduce back energy transfer losses.
View Article and Find Full Text PDFThe photophysical properties of the novel nonanuclear Tb(III) clusters Tb-L1 and Tb-L2 involving the ligands methyl 4-methylsalicylate (L1) and methyl 5-methylsalicylate (L2) are reported. The position of the methyl group has an effect on their photophysical properties. The prepared nonanuclear Tb(III) clusters were identified by fast atom bombardment mass spectrometry and powder X-ray diffraction.
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