Spectroscopic and computational studies of the solid state photophysical properties of a biscoumarin dye.

The solid state photophysical properties of the 3,3'-paraphenyl bis[6,8-dimethoxy-2H-chromen-2-one] symmetrical biscoumarin material were investigated by optical spectroscopy techniques and by theoretical calculations. Vibrational analysis using IR absorption and Raman scattering techniques carried out together with DFT theoretical calculations have confirmed the structure of this biscoumarin. The geometry optimization using different functionals reveal a nonplanar equilibrium structure with a dihedral between the phenyl and the pyran rings of about 142°. The UV-Visible absorption measurements and the TDDFT simulation show that this biscoumarin is characterized by a bicomponent feature resulting from ππ* electronic transitions and Intramolecular Charge Transfer (ICT). Solid state photoluminescence showed a bright blue-green emission at 506 nm with a large stokes shift estimated at 146 nm, and the temperature dependence study of this emission reveals two thermal evolution regimes. Finally, these good optical properties, as well as the stability of the emission, make this biscoumarin dye of potential interest for optoelectronic applications.

Down and up conversion luminescence of the lead-free organic metal halide material: (C9H8NO)2SnCl6·2H2O.

The present work deals with the optical properties of hybrid organic metal halide material namely (C9H8NO)2SnCl6·2H2O. Its structure is built up from isolated [SnCl6]2- octahedral dianions surrounded by Hydroxyl quinolinium organic cations (C9H8NO)+, abbreviated as [HQ]+. Unlike the usual hybrid materials, where metal halide ions are luminescent semiconductors while the organic ones are optically inactive, [HQ]2SnCl6·2H2O contains two optically active entities: [HQ]+ organic cations and [SnCl6]2- dianions. The optical properties of the synthesized crystals were studied by optical absorption spectroscopy, photoluminescence measurements and DFT calculations of electronic density of states. These studies have shown that both organic and inorganic entities have very close HOMO-LUMO gaps and very similar band alignments favoring the resonant energy transfer process. In addition, measurements of luminescence under variable excitations reveal an intense green luminescence around 497 nm under UV excitation (down conversion) and infrared excitation (up conversion luminescence). The down conversion luminescence is assigned to the π-π* transition within the [HQ] + organic cations involving charge transfer between the organic and inorganic entities, whereas the up-conversion luminescence is based on the triplet-triplet annihilation mechanism (TTA).

Sensitizer-free photon up conversion in (HQ)2ZnCl4 and HQCl crystals: systems involving resonant energy transfer and triplet-triplet annihilation.

This work deals with normal luminescence and up-conversion luminescence involving charge transfer and triplet-triplet annihilation in the lead free hybrid materials (HQ)2[ZnCl4] and HQCl salt; HQ is the hydroxyquinolate cation (HQ+ = C9H8NO+). The crystal structures were determined by X-ray diffraction and the optical properties were investigated by optical absorption and photoluminescence measurements and electronic band structure calculations. Under UV excitation, the normal luminescence is associated with π-π* transitions within the organic cation and involves energy and charge transfer between the inorganic ion and organic cation. Moreover, photoluminescence measurements under various excitation wavelengths performed on the hybrid (HQ)2[ZnCl4] and the salt HQCl have shown efficient up conversion of light from the near infrared (855 nm) to the visible region at 471 nm and 490 nm respectively. This behavior is described as sensitizer-free up-conversion luminescence based on the triplet-triplet annihilation process (TTA-UCL). These compounds are believed to be the first sensitizer-free TTA up-converting materials found in the organic metal halide family. Compared with the conventional TTA-UC solid systems based on precious and heavy metal organic complexes, the title compounds exhibit efficient photon up-conversion. Furthermore, they have extended the NIR conversion photons to a wide spectral interval of about 300 nm centred around 850 nm.

Interplay between a crystal's shape and spatiotemporal dynamics in a spin transition material.

We investigated by means of optical microscopy (OM) the spatiotemporal features of the thermo-induced spin transition of [Fe(2-pytrz)2{Pd(CN)4}]·3H2O (1) (2-pytrz = 4-(2-pyridyl)-1,2,4,4H-triazole) single crystals having two different shapes (triangle and rectangle). While magnetic and calorimetric measurements, performed on a polycrystalline material, showed the respective average heating and cooling transition temperatures of (Tdown1/2 ∼ 152 K, Tup1/2 ∼ 154 K) and (Tdown1/2 ∼ 160.0 K, Tup1/2 ∼ 163.5 K), OM studies performed on a unique single crystal revealed significantly different switching temperatures (Tdown1/2 ∼ 152 K and Tup1/2 ∼ 162 K). OM investigations showed an interface spreading over all crystals during the spin transition. Thanks to the color contrast between the low-spin (LS) and the high-spin (HS) states, we have been able to follow the real time dynamics of the spin transition between these two spin states, as well as access the thermal hysteresis loop of each single crystal. After image processing, the HS-LS interface's velocity was carefully estimated in the ranges [4.4-8.5] µm s-1 and [2.5-5.5] µm s-1 on cooling and heating, respectively. In addition, we found that the velocity of the interface is shape-dependent, and accelerates nearby the crystal's borders. Interestingly, we observed that during the propagation process, the interface optimizes its shape so as to minimize the excess of elastic energy arising from the lattice parameter misfit between the LS and HS phases. All of these original experimental results are well reproduced using a spatiotemporal model based on the description of the spin-crossover problem as a reaction diffusion phenomenon.

Rapid and robust spatiotemporal dynamics of the first-order phase transition in crystals of the organic-inorganic perovskite (C12H25NH3)2PbI4.

The dynamics of the thermally induced first-order structural phase transition in a high-quality single crystal of the organic-inorganic perovskite (C12H25NH3)2PbI4 was investigated by optical microscopy. The propagation of the straight phase front (habit plane) during the phase transition along the cooling and heating pathways of the thermal hysteresis was observed. The thermochromic character of the transition allowed monitoring of the thermal dependence of average optical density and aided the visualization of the interface propagation. The thermal hysteresis loop is 10 K wide, and the interface velocity is constant at V ≈ 1.6 mm s(-1). The transition is accompanied with sizeable change in crystal size, with elongation of ~6% along the b axis and compression of ~ -2% along the a axis, in excellent agreement with previously reported X-ray diffraction data. The progression of the habit plane is at least 160 times faster than in spin-crossover materials, and opens new prospects for organic-inorganic perovskites as solid switching materials. Moreover, the crystals of (C12H25NH3)2PbI4 are unusually mechanically robust and present excellent resilience to thermal cycling. These hitherto unrecognized properties turn this and possibly similar hybrid perovskites into perspective candidates as active medium for microscopic actuation.

Crystal structure, vibrational spectra and non-linear optical properties of diethylenetriammonium hexabromobismuthate: C4H16N3BiBr6.

A new organic-inorganic material, diethylenetriammonium hexabromobismuthate (C4H16N3)BiBr6, was synthesized and characterized by X-ray diffraction, infrared absorption, Raman spectroscopy scattering and optical absorption. The crystal lattice is composed of discrete [BiBr6] anions surrounded by diethylenetriammonium cations. The title compound crystallizes in the non-centro-symmetric space group P212121 of orthorhombic system. Theoretical calculations were performed using density functional theory (DFT) at B3LYP/LanL2DZ level of theory for studying the molecular structure, vibrational spectra and non-linear optical (NLO) properties of the investigated molecule in the ground state. Good consistency is found between the calculated results and the experimental structure, IR, and Raman spectra. The results also show that the title compound might have important NLO behavior and can be a potential new nonlinear optical (NLO) material of interest.

Molecular structure, NLO, MEP, NBO analysis and spectroscopic characterization of 2,5-dimethylanilinium dihydrogen phosphate with experimental (FT-IR and FT-Raman) techniques and DFT calculations.

Single crystals of 2,5-dimethylanilinium dihydrogen phosphate were grown by slow evaporation method at room temperature. The synthesized compound was characterized by powder X-ray diffraction analysis to confirm its crystalline nature. The optimized molecular structure, vibrational spectra and the optical properties were calculated by the density functional theory (DFT) method using the B3LYP function with the 6-31G(d,p) basis set. Theoretical simulation of infrared and Raman spectra led to excellent overall agreement with the observed spectral patterns. The complete assignments of the vibrational spectra were carried out with the aid of potential energy distribution (PED). The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis leading to high nonlinear optical (NLO) activity. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules.

Bis[tris(propane-1,3-diamine-κ(2) N,N')-nickel(II)] di-aqua-bis(propane-1,3-di-amine-κ(2) N,N')nickel(II) hexa-bromide dihydrate.

In the title compound, [Ni(C3H10N2)3]2[Ni(C3H10N2)2(H2O)2]Br6·2H2O, one Ni(2+) cation, located on an inversion centre, is coordinated by four N atoms from two ligands and by two water O atoms. The other Ni(2+) cation, located in a general position, is coordinated by six N atoms from three ligands. In both cases, the Ni(2+) cation has an octa-hedral coordination environment. The overall structural cohesion is ensured by three types of hydrogen bonds, N-H⋯Br, O-H⋯Br and O-H⋯O, which connect the two types of complex cations, the bromide counter-anions and the lattice water molecules into a three-dimensional network.

Vibrational spectroscopic study, charge transfer interaction and nonlinear optical properties of L-asparaginium picrate: a density functional theoretical approach.

Single crystals of L-asparaginium picrate (LASP) were grown by slow evaporation technique at room temperature and were the subject of an X-ray powder diffraction study to confirm the crystalline nature of the synthesized compound. FT-IR and Raman spectra were recorded and analyzed with the aid of the density functional theory (DFT) calculations in order to make a suitable assignment of the observed bands. The optimum molecular geometry, normal mode wavenumbers, infrared and Raman intensities and the first hyperpolarizability were investigated with the help of B3LYP method using 6-31G(d) basis set. The theoretical FT-IR and Raman spectra of LASP were simulated and compared with the experimental data. A good agreement was shown and a reliable vibrational assignment was made. Natural bond orbital (NBO) analysis was carried out to demonstrate the various inter and intramolecular interactions that are responsible for the stabilization of the title compound leading to high NLO activity. A study on the electronic properties was performed by time-dependent DFT (TD-DFT) approach. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules.

Molecular structure, vibrational spectra and nonlinear optical properties of 2,5-dimethylanilinium chloride monohydrate: a density functional theory approach.

Single crystals of 2,5-dimethylanilinim chloride monohydrate were grown by slow evaporation at room temperature and were characterized by X-ray powder diffraction study to confirm the crystalline nature of the synthesized compound. The optimized molecular structure, vibrational spectra and the optical properties were calculated by the density functional theory (DFT) method using the B3LYP function with the 6-31G(d,p) basis set. Simulation of infrared and Raman spectra led to excellent overall agreement with the observed spectral patterns. The complete assignments of the vibrational spectra were carried out with the aid of potential energy distribution (PED). The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis leading to high nonlinear optical (NLO) activity. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules.

Vibrational spectra, optical properties, NBO and HOMO-LUMO analysis of L-Phenylalanine L-Phenylalaninium Perchlorate: DFT calculations.

In this work, we report a combined experimental and theoretical study of a nonlinear optical material, L-Phenylalanine L-Phenylalaninium Perchlorate. Single crystals of the title compound have been grown by slow evaporation of an aqueous solution at room temperature. Theoretical calculations were preceded by redetermination of the crystal X-ray structure. The compound crystallizes in the non-centro symmetric space group P2(1)2(1)2(1) of the orthorhombic system. The FT-IR and Raman spectra of the crystal were recorded and analyzed. The density functional theory (DFT) computations have been performed at B3LYP/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensity and NLO properties. All observed vibrational bands have been discussed and assigned to normal mode or to combinations on the basis of our DFT calculations as a primary source of attribution and also by comparison with the previous results for similar compounds. Natural bond orbital analysis was carried out to demonstrate the various inter-and intramolecular interaction that are responsible of the stabilization of the compound. The lowering of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap appears to be the cause of its enhanced charge transfer interaction leading to high NLO activity.

Vibrational spectral studies and non-linear optical properties of L-leucine L-leucinium picrate: a Density Functional Theory approach.

Single crystals of l-leucine l-leucinium picrate were grown by slow evaporation at room temperature and were characterized by X-ray powder diffraction study to confirm the crystalline nature of the synthesized compound. The optimized molecular structure, vibrational spectra and the optical properties were calculated by the Density Functional Theory (DFT) method using the B3LYP function with the 6-31G(d) basis set. Good consistency is found between the calculated results and the experimental structure, IR, and Raman spectra. The detailed interpretation of the vibrational modes was carried out. The natural bond orbital (NBO) analysis, confirms the occurrence of intermolecular hydrogen bonds that are responsible for the stabilization of the title compound, leading to high nonlinear optical (NLO) activity. The lowering in the HOMO and LUMO energy gap explains the eventual charge transfer interactions that take place within the molecules.