Polarized Luminescence Spectra Research Articles

Synthesis and Characterization of Asymmetric Azatwistarenes with Chiroptical Property.

Three novel azatwistarenes 5a, 8, and 13 have been synthesized via the Povarov reaction and fully characterized. All of the enantiomers were separated using chiral high-performance liquid chromatography, and their optical properties were investigated through circular dichroism and circularly polarized luminescence spectra. In addition, such desired azatwistarenes have a positive response to acid in dichloromethane.

Polarized photoluminescence and g-factor in an inhomogeneous ensemble of quantum dots in magnetic fields

In this work, polarized photoluminescence caused by quasi-equilibrium spin orientation of excitons at Zeeman sublevels in an ensemble of quantum dots of different sizes is studied theoretically. The following unexpected results are found: (i) the splitting of photoluminescence bands in a magnetic field in an ensemble of quantum dots is much larger than the Zeeman splitting of exciton levels in a single dot, (ii) contrary to the Boltzmann distribution the low-energy luminescence band has a lower intensity than the high-energy band, (iii) the sign of the circular polarization of photoluminescence changes along the contour of the bands, (iv) a universal formula for the dependence of the exciton g-factor on the quantum dot size is obtained. All of the above features of the polarized luminescence spectra are explained by variations of the exciton g-factor when its quantization energy changes. The results obtained are applicable not only to ensembles of quantum dots, but also to any ensemble of localized states: excitons in quantum wells under conditions of well-width fluctuations, impurity states in quantum wells, etc.

Ball Pivoting Algorithm and discrete gaussian curvature: A direct way to curved nanographene circularly polarized luminescence spectral simulation

Theoretical innovations for constructing robust computational protocols are of fundamental significance for a variety of advanced chiroptical spectroscopies. The new generation of chiral curved nanographenes offered us the opportunity to study the chiral emission phenomena in the nanometers scale. Herein we reported a distinctive method that combines topological aspects and the density functional theory in order to reach a coherent description of calculated circularly polarized luminescence spectra of negatively curved nanographenes. Our computational plan was defined as a multi-sequence strategy, paying the attention on the relationship between the molecular curvature and the relative spectroscopic properties: 1) the Ball Pivoting Algorithm for the nanographene surface reconstruction; 2) the atom by atom discrete gaussian curvature analysis to establish which DFT functional better approximates the shape of nanographenes backbones; 3) molecular dynamics in the first excited state for accounting the thermal effect; 4) TDDFT benchmark to scrutinize which functional provides the most reliable excitation energies and rotatory strengths for an accurate CPL spectral simulation. The direct merging of the previous steps celebrated the B3LYP (coupled with the 6-311G(d,p) basis set) as the most precise exchange–correlation functional in duplicating exquisitely the CPL profiles of a heterogeneous set of functionalized nanographene.

Synthesis and Stereodynamic and Emission Properties of Dissymmetric Bis-Aryl Carbazole Boranes and Identification of a CPL-Active B–C Atropisomeric Compound

We synthesized bis-aryl carbazole borane derivatives having emissive properties and axial chirality. The resolution of a thermally stable atropisomeric pair (compound 1b), due to a B-C chiral axis, was achieved by chiral stationary-phase high-performance liquid chromatography (CSP-HPLC). Complete photophysical properties of all compounds were measured and simulated by time-dependent density functional theory (TD-DFT) calculations of the complete fluorescence cycle, and circularly polarized luminescence spectra were obtained for the atropisomers of compound 1b, whose absolute configuration was derived using a TD-DFT simulation of the electronic circular dichroism (ECD) spectra.

Growth, spectroscopy and CW laser operation of Ho3+ doped CaY0.9Gd0.1AlO4 single crystal

Ho3+-doped CaY0.9Gd0.1AlO4 single crystal was successfully grown by the Czochralski technique for the first time. The polarized absorption spectra, polarized luminescence spectra and fluorescence decay curve of the crystal were investigated at room temperature. The spectroscopic parameters are calculated based on Judd–Ofelt theory, the values of Ω2,4,6 were calculated to be 3.16 × 10−20 cm2, 3.93 × 10−20 cm2, 0.91 × 10−20 cm2, respectively. The Ho:CaY0.9Gd0.1AlO4 crystal exhibits strong emission at 2013 nm for π- and 2032 nm for σ-polarizations with stimulated emission cross section of 6.64 × 10−20 cm2 and 1.90 × 10−20 cm2, respectively. The fluorescence lifetime of the 5I7 level was measured to be 6.60 ms. The continuous-wave (CW) laser operation of Ho:CaY0.9Gd0.1AlO4 crystal around 2 μm was demonstrated.

Chiral superstructures of inorganic nanorods by macroscopic mechanical grinding

The development of mechanochemistry substantially expands the traditional synthetic realm at the molecular level. Here, we extend the concept of mechanochemistry from atomic/molecular solids to the nanoparticle solids, and show how the macroscopic grinding is being capable of generating chirality in self-assembled nanorod (NR) assemblies. Specifically, the weak van der Waals interaction is dominated in self-assembled NR assemblies when their surface is coated with aliphatic chains, which can be overwhelmed by a press-and-rotate mechanic force macroscopically. The chiral sign of the NR assemblies can be well-controlled by the rotating directions, where the clockwise and counter-clockwise rotation leads to the positive and negative Cotton effect in circular dichroism and circularly polarized luminescence spectra, respectively. Importantly, we show that the present approach can be applied to NRs of diverse inorganic materials, including CdSe, CdSe/CdS, and TiO2. Equally important, the as-prepared chiral NR assemblies could be served as porous yet robust chiral substrates, which enable to host other molecular materials and induce the chirality transfer from substrate to the molecular system.

Modeling Absorption and Emission Spectroscopies of Symmetric and Asymmetric Azaoxahelicenes in Vacuum and Solution

Helicenes are of general interest due to the significant chiral signals in both absorption- and emission-based spectroscopy. Herein, the spectroscopic properties of four recently synthesized azaoxahelicenes are studied using density functional theory methods. The azaoxahelicenes have 7, 9, 10, and 13 units and one to two complete turns of the structure. UV-vis absorption and electronic circular dichroism spectra are determined both in vacuum and in solution using explicit solvation through a combined molecular dynamics/polarizable embedding framework. Additionally, emission and circularly polarized luminescence spectra are determined based on vibronic calculations. The resulting spectra are in good agreement with the experimentally available data, highlighting that both absorption- and emission-based spectra of the systems can be modeled computationally such that reliable predictions can be made for systems that are yet to be synthesized.

Er<sup>3+</sup>,Yb<sup>3+</sup>:YGdSiO<sub>5</sub> Crystal as Gain Media for Lasers Emitting in the Spectral Range of 1.5–1.6 µm

Solid-state erbium lasers, emitting in the spectral range of 1.5–1.6 µm, are of great interest for several industrial applications. Nowadays the Er:glass is the most widespread laser material for obtaining laser radiation at the wavelength near 1.5 µm. However, the maximal output powers of such lasers are restricted by hundreds of milliwatts because low thermal characteristics of the glass host. By this reason the search for new crystalline hosts doped with erbium ions is the actual task.In this article the investigation results of spectroscopic properties of Er3+,Yb3+:YGdSiO5 (YGSO) crystals are reported. Polarized absorption and luminescence spectra were measured. The lifetimes of energy levels were determined. The excited state absorption spectra were measured. It was shown that excited state absorption band does not overlap with gain band in the range 1.5–1.6 µm. The energy transfer efficiency from ytterbium to erbium ions was estimated. The stimulated emission and gain cross-section spectra for Er3+ ions in YGSO were calculated.

Polarization and temperature studies of the spectral luminescent properties of Er:LiNbO3 ceramics on Yb substrate, Er:LiNbO3

The present paper features experimental data on temperature studies of polarized luminescence spectra of Er:LiNbO3 ceramics deposited by laser ablation on the surface of a single-crystal Yb,Er:LiNbO3 substrate. It is shown that the formation of whiskers in the deposited layer of Er0.1-0.2:LiNbO3 ceramics enhances the polarization dependence of the luminescence spectra and affects the transition rates of relaxation channels in favor of the σ component of the pump radiation.

Growth, spectroscopy and laser operation of monoclinic Nd:CsGd(MoO4)2 crystal with a layered structure

We report on the growth, structure, polarized spectroscopy and first laser operation of a double molybdate compound featuring a layered structure – the monoclinic Nd:CsGd(MoO4)2. Single-crystals of 3 at.% Nd:CsGd(MoO4)2 are grown from the flux using cesium trimolybdate (Cs2Mo3O10) as a solvent. They crystallize in the monoclinic system (sp. gr. P2/c) with lattice constants a = 9.5239(4) Å, b = 5.0752(5) Å, c = 8.0580(7) Å and β = 91.157(9)°. Nd:CsGd(MoO4)2 exhibits a perfect cleavage along the (100) plane. Polarized absorption and luminescence spectra of the Nd3+ dopant ion are measured. The maximum stimulated-emission cross-section is 29.0 × 10−20 cm2 at 1065.9 nm for light polarization E ||b. The luminescence lifetime is 145 μs. The transition probabilities are determined using the modified Judd-Ofelt theory yielding the intensity parameters Ω2 = 26.736, Ω4 = 12.736 and Ω6 = 17.771 [10−20 cm2] and α = 0.122 [10−4 cm]. Continuous-wave laser operation is achieved in cleaved single-crystal plates of Nd:CsGd(MoO4)2 yielding a maximum output power of 0.54 W at 1066 nm with a laser threshold of 70 mW, a slope efficiency η of 60.4% and a linearly polarized laser output (E ||b).

Multiple Fused Anthracenes as Helical Polycyclic Aromatic Hydrocarbon Motif for Chiroptical Performance Enhancement.

Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π-conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt-catalyzed cycloisomerization of the corresponding ethynyl-substituted precursors. The nonplanar and helical structure was confirmed by X-ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol-1 . The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δϵ| 1380 L mol-1 cm-1 ) and CPL (|glum | 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time-dependent DFT calculations.

Growth, spectroscopic features and efficient 2 μm continuous-wave laser output of a Tm3+: Gd0.1Y0.9AlO3 disordered crystal

Tm3+-doped Gd0.1Y0.9AlO3 (GYAP) disordered crystal with size of Φ (28–35) mm × (50–70) mm was grown successfully by the Czochralski method. The X-ray powder diffraction, polarized absorption spectra, and polarized luminescence spectra of Tm3+: GYAP crystal were measured to investigate the structural and luminescent properties of the crystal. The cell parameters of Tm3+: GYAP crystal were found to be a = 5.321 Å, b = 7.371 Å, and c = 5.176 Å, respectively. The spectral parameters such as line strengths, Judd-Ofelt (J-O) intensity parameters Ω2,4,6, the radiative transition rates, the branching ratios, and the radiative lifetimes were calculated based on the J-O theory. The absorption cross-sections were determined to be 0.47 × 10−20 cm2 (at 797 nm), 0.55 × 10−20 cm2 (at 777 nm), and 0.41 × 10−20 cm2 (at 794 nm), respectively. The Tm3+: GYAP crystal, as far as we know, was firstly used for laser demonstration with a 793 nm laser diode (LD). The slope efficiency up to 6.4% was achieved with maximum output power of 426 mW at 1941.953 nm. The resulting linear polarized and stable laser output indicate that the Tm3+: GYAP disordered crystal can be applied to achieving tunable and ultra-short laser at ~2 μm.

Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes.

Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study, C2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1-CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their 1Lb and 1La transitions (|Δε| = 10-12 and 51-57 M-1 cm-1, respectively), while intense CEs were notified in their 1B transitions (|Δε| = 156-216 M-1 cm-1), absorption dissymmetry (gabs) factors being in orders of 10-2. Circularly polarized luminescence spectrum was also obtained for cyanamide derivative CZ1, with a comparative luminescence dissymmetry (glum) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivative CZ2.

Vibrationally resolved electronic circular dichroism and circularly polarized luminescence spectra of a boron-fused double helicene: A theoretical study.

In this work, we present the theoretical study of the vibrationally resolved absorption (ABS), electronic circular dichroism (ECD), emission (EMI), and circularly polarized luminescence (CPL) spectra of a boron-fused double helicene, with a detailed and complete discussion of the alternative possible approximate methods. Given the fact that few examples of CPL calculations exist, the potential energy surfaces (PESs) have been constructed and compared with Adiabatic (AH) and Vertical Hessian (VH) models. All the vibronic calculations have accounted for Duschinsky mixings, Franck-Condon (FC) effect and Herzberg-Teller (HT) contribution. Moreover, different HT expansions have been checked and compared, by computing the derivatives of the electric and magnetic dipole transition moments around the equilibrium geometries of the initial and final states. Our results show that both AH and VH models have well reproduced the experimental vibronic structures and VH model shows a better performance in the simulation of spectral lineshapes. They also show that HT effects dominate the shapes of EMI and CPL, tuning the relative heights of the different vibronic peaks, improving the agreement with the experiment for EMI. Moreover, HT effects are the main reason for the mirror-symmetry breaking between ECD and CPL spectra. Furthermore, interesting interference effects between FC and HT contributions have also been addressed.

Aqueous Photon Upconversion by Anionic Acceptors Self-Assembled on Cationic Bilayer Membranes with a Long Triplet Lifetime

Anionic 9,10-diphenylanthracene chromophores electrostatically bound to cationic, chiral bilayer membranes show ordered self-assembly in water. The integrity of the chromophore-accumulated aqueous bilayer membranes is ensured by multiple hydrogen-bond networks introduced in the bilayer, which allowed adaptive accommodation of the guest chromophores at the inner surface of the bilayer while maintaining their cohesive interactions. The regular chromophore alignment in the aqueous assembly is confirmed by differential scanning calorimetry, circular dichroism, and circularly polarized luminescence spectra. Excitonic migration of triplet energy occurs among the chromophores densely organized at the inner surface of the bilayer, which lead to triplet–triplet annihilation-based photon upconversion (TTA-UC). This acceptor-bilayer self-assemblies show a notably long triplet lifetime of 8.0 ms, which allows TTA-UC at sufficiently low excitation light intensity. These results demonstrate the usefulness of the simple electrostatic accumulation approach for TTA-UC chromophores where the suitable molecular design of the TTA-UC chromophore-integrated bilayer membranes plays a key role.

L-Stercobilin-HCl and d-Urobilin-HCl. Analysis of Their Chiroptical and Conformational Properties by VCD, ECD, and CPL Experiments and MD and DFT Calculations.

Vibrational circular dichroism (CD) and IR spectra of dichloromethane solutions of l-stercobilin and d-urobilin hydrochlorides have been recorded in the mid-IR region. The spectra are best interpreted by combining molecular dynamics calculations and density functional theory (DFT) calculations within the quantum mechanics/molecular mechanics ONIOM-type framework, and the combined predicted results are better and more informative than the more standard analysis provided by DFT calculations. The same approach also sheds light on the Cotton effect sign inversion of room temperature versus low-temperature electronic CD spectra of the same compounds in methanol-glycerol solution. Finally, circularly polarized luminescence spectra for l-stercobilin in chloroform solution provide information on the excited-state geometry of this molecule.

Photon Density of States in a Cholesteric Photonic Crystal

The photon density of states in a cholesteric photonic crystal in the region of the photon band has been determined from the measured polarized luminescence spectra. The orientational ordering of the transition dipole moment in luminescence, as well as the ellipticity of light eigenmodes in the photonic crystal, has been taken into account when determining the density of states. Maxima in the spectrum of the density of states on two sides of the photonic band are related to the displacement of states from the band. The group velocity of light inside the photonic band exceeds the speed of light in vacuum.

Hierarchical Self-Assembly and Chiroptical Studies of Luminescent 4d-4f Cages.

Multinuclear lanthanide-containing supramolecular cages have received increasing attention recently because of their unique electroptical and magnetic properties. Here we report the hierarchical self-assembly and chiroptical studies of a group of 4d-4f heterometallic cages synthesized from a preformed dimetalloligand [(bpy)2Pd212]2+ (2) (bpy = 2,2-bipyridine) and a variety of trivalent lanthanide ions (Ln = NdIII, EuIII, YbIII). The programmable self-assembly process leading to the trigonal bipyramidal cages formulated as {Ln2[(bpy)2Pd212]3}12+ (3) has been confirmed by one- and two-dimensional NMR, electro-spray-ionization time-of-flight mass-spectroscopy, and in one typical case by single-crystal X-ray diffraction studies. Circular dichroism and circular polarized luminescence spectra confirmed the strict control of stereoselectivity on the heterometallic cages, dictated by the chiral amide groups on the ligands. Excitation (up to 420 nm) on the dipalladium chromophores on these cages leads to the characteristic lanthanide luminescence at both the visible and the near-infrared regions, depending on the lanthanide ions used. Through the assembly-disassembly process, luminescent turn-off sensing toward penicillin among several widely used antibiotics has also been demonstrated with the Europium cage, featuring a limit of detection as low as 0.88 ppb (S/N = 3). Our results pave the way for the construction of chiral 4d-4f supramolecular cages which may find potential applications in luminescent sensing and/or labeling reagents.

Synthesis, Optical Resolution, and Circularly Polarized Luminescence of an Axially Chiral Porphyrin Dimer

AbstractMotivated by the chiral supramolecular structures of chlorophylls in photosynthesis proteins, i. e., special pairs present in purple photosynthetic bacteria, photosystems‐I, and ‐II, a chiral porphyrin dimer was designed, synthesized, and resolved to give optically pure forms. Synthesis of the dimer was achieved by using 5,10‐diarylporphyrin as the starting material. The stereochemistry of the dimer was speculated by comparing experimentally and theoretically obtained circular dichroism spectra. Clear circularly polarized luminescence spectra were obtained at 636 nm with dimensionless Kuhn's anisotropy value of ∼2.0 × 10−3.

Growth, spectroscopy and continuous-wave laser performance of Nd3+:LiLu0.65Y0.35F4 crystal

A mixed fluoride crystal of LiLu0.65Y0.35F4 doped with Nd3+ ions was grown by the Bridgman–Stockbarger method. Polarized absorption and luminescence spectra as well as luminescence lifetime were measured at room temperature. Emission probabilities, branching ratios and radiative lifetime were studied within the Judd–Ofelt theory and the emission cross section spectra were calculated. Efficient continuous wave laser operation was demonstrated with the crystal. A maximum output power of 7.7 W and slope efficiency of 60% were achieved at 1047 nm for the TEM00 mode.