Circularly Polarized Luminescence from Schiff-base [4]Helicene Boron Complexes.

Boron complexes with Schiff-base [4]helicene ligands were synthesized. These complexes were characterized by NMR spectroscopy and their helical molecular structures were unequivocally established by X-ray diffraction (XRD) analysis. The helical boron complexes exhibited efficient photoluminescence under UV irradiation, and the circularly polarized luminescence (CPL) properties were investigated for optically pure samples. Density functional theory (DFT) calculations were conducted to further understand their photophysical properties including chiroptical responses.

External magnetic field-induced circularly polarized luminescence and electroluminescence from optically inactive thermally activated delayed fluorescence material 4CzIPN.

An achiral optically inactive organic luminophore, 4CzIPN, exhibits circularly polarized thermally activated delayed fluorescence when photoexcited under an external magnetic field. By embedding this luminophore in an active emission layer, an external-magnetic-field-induced circularly polarized electroluminescent device is developed in this study. The Faraday geometry of the applied magnetic field completely controls the direction of rotation of 4CzIPN-derived circularly polarized luminescence and electroluminescence.

Single Molecular Persistent Room-Temperature Phosphorescence and Circularly Polarized Luminescence from Binaphthol-Decorated Optically Innocent Cyclotriphosphazenes.

Circularly polarized luminescence (CPL) features of BINOL-decorated cyclotriphosphazenes (CPs) are reported for the first time. The luminescence dissymmetry factor (glum ) of these compounds in chloroform solutions and polymethyl methacrylate (PMMA) thin films with wt 1 % doping concentrations are found to be 1.0×10-3 , and 2.9×10-3 , respectively. However, no CPL signal is observed for the pristine solids. The enantiomers (CP-(R)/CP-(S)) show ultraviolet photoluminescence (~350-360 nm) in solution and the solid state. These compounds show ~10 times larger absolute photoluminescence quantum yield (PLQY) than the simple BINOLs in the solutions state. In the solid state, CP-(R) shows larger PLQY than binaphthol-(R); in contrast, the S enantiomer shows lower PLQY than binaphthol-(S); this indicates that the isomer-dependent solid-state packing of these compounds plays a crucial role in controlling the PL. Thin films with more than 1 % doping concentration and pristine solids of these compounds do not show persistent room-temperature phosphorescence (pRTP) due to concentration-caused quenching. However, thin films with wt 1 % of these chiral emitters exhibit pRTP characteristics with a ~159-343 ms lifetime under vacuum. Theoretical calculations reveal that the cyclophosphazene acts as an optically innocent dendritic core, and the optical features of these compounds are dictated by the pendent BINOL chromophore.

External environment sensitive circularly polarized luminescence properties of a chiral boron difluoride complex.

A chiral Schiff-base boron difluoride complex bearing a diethylamino group was synthesized. Its photophysical properties were investigated and compared with those of its non-substituted analogue. The complex was found to exhibit solvatofluorochromism with bluish-white emission in moderately polar solvents and intense blue emission in nonpolar solvent. Circularly polarized luminescence (CPL) properties were also examined and it was found that the absolute value of the luminescence dissymmetry factor (g lum) increases significantly in the KBr-dispersed pellet state compared to the solution state. Notably, CPL intensity of the complex enhanced approximately three times upon addition of CH3SO3H in CH2Cl2. Density functional theory (DFT) calculations were conducted to further understand the photophysical properties.

Sign control of circularly polarized luminescence of chiral Schiff-base Zn(II) complexes through coordination geometry changes.

The handedness of circularly polarized luminescence (CPL) of Zn(II) complexes with a chiral Schiff-base ligand can be controlled by coordination geometry changes in solution and in the solid state. The relationships between molecular structure and chiroptical properties were discussed with the results of X-ray diffraction analysis and DFT calculations.

Crystallization induced room-temperature phosphorescence and chiral photoluminescence properties of phosphoramides.

We report the design and synthesis of a series of room temperature phosphorescent phosphoramides TPTZPO, TPTZPS, and TPTZPSe with a donor (phenothiazine)-acceptor (P = X, X = O, S, and Se) architecture. All the compounds show structureless fluorescence with a nanosecond lifetime in dilute solutions. However, these compounds show dual fluorescence and room temperature phosphorescence (RTP) in the solid state. Both the intensity and energy of luminescence depend on the heteroatom attached to the phosphorus center. For example, compound TPTZPO with the P[double bond, length as m-dash]O unit exhibits fluorescence at a higher energy region than TPTZPS and TPTZPSe with the P[double bond, length as m-dash]S and P[double bond, length as m-dash]Se groups, respectively. Crystalline samples of TPTZPO, TPTZPS, and TPTZPSe show stronger RTP than the amorphous powder of respective compounds. Detailed steady-state, time-resolved photoluminescence and computational studies established that the 3n-π* state dominated by the phenothiazine moiety is the emissive state of these compounds. Although TPTZPS and TPTZPSe crystallized in the chiral space group, only TPTZPSe showed chiroptical properties in the solid state. The luminescence dissymmetry factor (g lum) value of TPTZPS is small and below the detection limit, and a CPL spectrum could not be observed for this compound.

Multi-colour circularly polarized luminescence properties of chiral Schiff-base boron difluoride complexes.

A series of chiral Schiff-base boron difluoride complexes was synthesized and their photophysical properties were examined. These complexes showed multi-colour (blue, yellow and red) photoluminescence in solution and in the solid state with good emission quantum yield (Φ) depending on the π-systems of the ligands. The chiral complexes exhibited circularly polarized luminescence (CPL) with an absolute luminescence dissymmetry factor (glum) of up to the 1.3 × 10-3 in solution and 1.9 × 10-2 in the drop-cast film state. Density functional theory (DFT) and time-dependent (TD) DFT calculations were conducted to further understand the photophysical properties.

Helical Oligophenylene Linked with [2.2]Paracyclophane: Stereogenic π-Conjugated Dye for Highly Emissive Chiroptical Properties.

A stereogenic π-system based on dimer (2) and trimer (3) of [2.2]paracyclophane (PC) and biphenyl was prepared and its structural, photophysical, and chiroptical properties were investigated. X-ray analysis revealed that the quaterphenyl moieties in 2 adopt a double helical structure anchoring [2.2]PC from both sides. Furthermore, 3 forms a isosceles triangle structure with a large chiral cavity. A homodesmotic reaction using DFT calculations revealed that 2 has a larger strain energy than 3 owing to its highly twisted phenylene linkers. Electronic and circular dichroic (CD) spectra were recorded in CH2 Cl2 solution. The spectra of both 2 and 3 are similar, and their longest absorption band accompanying a remarkable Cotton effect is attributed to the transition from HOMO to LUMO, which is delocalized to the quaterphenyl moiety. These compounds exhibit fairly high fluorescence quantum yields (ϕ=0.70-0.83) and moderate dissymmetry factor (|gCPL |=1.6×10-3 ) in circularly polarized luminescence (CPL).

Sign dependence of MCPL spectra on type and position of substituent groups of pyrene and phenanthrene derivatives.

Diamagnetic achiral pyrene and phenanthrene derivatives substituted with electron-donating hydroxyl/methoxy groups and electron-withdrawing carboxylic acid groups exhibited clear magnetic circularly polarised luminescence (MCPL) spectra at 360-460 nm in dilute solvents upon the application of N-up and S-up Faraday geometries under an external magnetic field of 1.6 T. Their MCPL signs were also susceptible upon application of the same Faraday geometry.