Nonlinear optical absorption and fluorescence of phosphine-substituted bithiophenes in the violet-blue spectral region

The nonlinear optical absorptions of two 5,5′-bis(diphenylphosphino)-2,2′-bithiophene derivatives, Ph₂(X)P(C₄H₂S)₂P(X)Ph₂ (X = O, 1; S, 2), have been investigated by direct transmission measurement with both picosecond and nanosecond laser pulses from 420 nm to 480 nm. Saturated dichloromethane solutions of 1 and 2 exhibit strong nonlinear optical absorptions in this violet-blue spectral region with that of 2 being stronger at all wavelengths. In the picosecond regime, at 420 nm, the transmittance rapidly falls to 50% when the incident fluence is 0.22 J/cm² for 1 and 0.11 J/cm² for 2. Two-photon absorption appears to be the primary mechanism for this nonlinear absorption. The two-photon absorption coefficients β for 1 (2.1 cm/GW) and 2 (4.4 cm/GM) were obtained by fitting the measurement of transmittance as the function of incident beam intensity at 420 nm. These β values are comparable with some of the best results obtained for organic materials in the green, red and infrared spectral region. Both compounds also show fluorescence with an emission peak at 390 nm for 1 and 400 nm for 2. The fluorescence of 1 is considerably stronger than is that of 2. The combination of the wide band gap and strong fluorescence emission of 1 makes it a promising candidate as a host material for blue organic light emitting diodes.     

Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (∼200 mJ/cm²) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm² exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.     

Photoconductivity of thin organic films

Thin organic films were deposited on silicon oxide surfaces with golden interdigitated electrodes (interelectrode gap was 2 μm), and the film resistivities were measured in dark and under white light illumination. The compounds selected for the measurements include molecules widely used in solar cell applications, such as polythiophene (PHT), fullerene (C₆₀), pyrelene tetracarboxylic diimide (PTCDI) and copper phthalocyanine (CuPc), as well as molecules potentially interesting for photovoltaic applications, e.g. porphyrin-fullerene dyads. The films were deposited using thermal evaporation (e.g. for C₆₀ and CuPc films), spin coating for PHT, and Langmuir-Schaeffer for the layer-by-layer deposition of porphyrin-fullerene dyads. The most conducting materials in the series are films of PHT and CuPc with resistivities 1.2 × 10³ Ω m and 3 × 10⁴ Ω m, respectively. Under light illumination resistivity of all films decreases, with the strongest light effect observed for PTCDI, for which resistivity decreases by 100 times, from 3.2 × 10⁸ Ω m in dark to 3.1 × 10⁶ Ω m under the light.     

Indium-induced superstructures formed on Si(1 1 0) surfaces

Si(1 1 0) surfaces covered with small amounts of In deposit and then annealed at high temperature were investigated by RHEED, and two kinds of superstructures with A = 3a and B = −a + 4b, and A = 3a − 2b and B = −2a + 4b as primitive translational vectors are reported to form on the surfaces.     

Supramolecular selectivity of [60]-fullerene among equivalently photoactive porphyrins

The photophysical investigation of different para-substituted tetraphenylporphyrins (TP), viz., meso-tetra(4′-hydroxyphenyl)-21H-23H-porphyrin(1),meso-tetrakis(4′-hex-5-enyloxyphenyl)-21H-23H-porphyrin(2), meso-tetrakis(4′-oct-7-enyloxyphenyl)-21H-23H-porphyrin(3) and meso-tetrakis(4′-undecyloxyphenyl)-21H-23H-porphyrin (4) revealed that except for quantum yield (φ) the para-substitution has little effect on any other photophysical properties like lifetime, excitation, emission wavelength, etc. The host-guest type interactions of these tetraarylporphyrins (TP 1-4), with [60]-fullerene (F) have been studied with ¹H NMR and fluorescence spectrometric techniques in carbon tetrachloride medium. Fluorescence studies revealed that the Q band of the TPs was sufficiently quenched upon addition of F. All the fullerene/porphyrin systems were found to produce stable complexes with 1:1 stoichiometry. Binding constants (K) of all the fullerene/porphyrin complexes have been determined by fluorescence quenching method. The association constant values for 1/F have been determined from plots of the Stern-Volmer equation (103.713×10⁴) and the Benesi-Hildebrand equation (110.440×10⁴). It has been observed that the insertion of long chain oxo-alkenyl/alkyl group in the para position of TPs in 2, 3 and 4 diminished the K values for F by two, four and even ten times with respect to that of 1. The observed trend in variation of the binding constants was supported by a gradual variation in the shift of ¹H NMR signal when measurements were carried out in CDCl₃.     

An asymmetric imidazole derivative as potential fluorescent chemosensor for Fe in aqueous solution

A novel conjugated molecule, L, based on 2,4,5-triphenylimidazole and 6-phenyl-2,2′-bipyridine (HC^∧N^∧N) was synthesized in two steps. The molecule can recognize Fe³⁺ in aqueous solution (THF/H₂O, 1/1, v/v) by the appearance of new emission bands at 416 and 442 nm, which can be attributed to the emission of the newly formed L-Fe³⁺ complex. The binding constant of the complex was calculated to be (6.6±0.39)×10³ M⁻¹, and its formation was also confirmed by the appearance of isosbestic points at 312 and 381 nm in the UV-visible spectral titration experiment. While other transition and rare-earth metal ions, such as Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Eu³⁺ and Nd³⁺, can only cause some decrease of L's fluorescence, alkali and alkaline earth metal ions, such as Li⁺, Na⁺, K⁺, Mg²⁺ and Ca²⁺, almost have no effect on L's fluorescence. The fluorescence of L can be recovered by the addition of EDTA to the L-Fe³⁺ system just due to EDTA's stronger chelating ability than that of L.     

Synthesis and luminescent properties of two Schiff-base boron complexes

Schiff bases N,N′-o-phenylenebis (salicylideneimine) (H₂L¹), N,N′-p-phenylenebis (salicylideneimine) (H₂L²) and their corresponding boron complexes (BF₂)₂L¹, (BF₂)₂L² were synthesized, respectively. The two boron complexes have been characterized by ¹H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF₂)₂L¹ (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF₂)₂L² (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.     

A novel coumarin-based switching-on fluorescent and colorimetric sensor for F

A novel turn-on fluorescent and colorimetric sensor, N-(4′-nitrophenyl)-2-oxo-6-(phenylazo)-2H-chromene-3-carbohydrazide (1), for fluoride in dimethyl sulfoxide (DMSO) was designed and synthesized. The binding ability evaluated by UV-vis and fluorescence titration experiments reveals that 1 can selectively recognize fluoride. In particular, addition of F⁻ to the DMSO solution of 1 resulted in an enhancement in fluorescence intensity at 338 and 352 nm, which can provide a way of ‘naked-eye’ detection for fluorides. The spectral change of 1 is due to the anion-induced increase of the charge density in and the rigidity of the host molecule. Furthermore, the binding mode with F⁻ was investigated by ¹H NMR experiments.     

Photoluminescent properties of heteroleptic cyclometalated platinum(II) complexes bearing 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dionate as an ancillary ligand

A new series of heteroleptic cyclometalated platinum(II) complexes Pt-1a-f was synthesized, employing 2-arylpyridine (or 1-arylisoquinoline) (HC^∧N-1) and 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dione (HO^∧O-1) for cyclometalation and as ancillary ligands, respectively, and photoluminescent properties were investigated. Focusing on red-shifted phosphorescence, C^∧N ligands containing π-extended aromatics and electron-rich heterocycles were examined. All obtained complexes exhibited photoluminescence at ambient temperature, and the emission maxima ranged from green (λ_PL=518 nm) to far red (λ_PL=708 nm). The large Stokes shifts of more than 100 nm and sub-microsecond or microsecond emission lifetimes revealed that these complexes are phosphorescent emissive. The quantum yield of Pt-1 ranged from 0.02 to 0.59 at ambient temperature and decreased as the emission maximum was red-shifted. In comparison with the reference platinum(II) complexes, Pt-2 bearing an aliphatic ancillary ligand, such as 2,2,6,6-tetramethylheptane-3,5-dionate (O^∧O-2), the ligand O^∧O-1 did not significantly affect the photoluminescence emission maxima, indicating that the energy gap between the singlet ground state and the triplet level was predominantly dependent on the C^∧N ligand.     

Sensitized luminescence properties of dinuclear lanthanide macrocyclic complexes bearing a benzophenone antenna

Dinuclear lanthanide (Ln=Tb³⁺ or Eu³⁺) complexes (Ln₂L2) of two octadentate macrocyclic polyaminopolycarboxylic ligands connected through a benzophenone (BP) moiety (L2) have been synthesized. Sensitized luminescence properties of Ln₂L2 in water have been studied in comparison to those of BP-conjugated mononuclear Ln complexes (LnL1). The luminescence intensity of Tb₂L2 is lower than that of TbL1 because of lower triplet quantum yield of the BP moiety. In contrast, Eu₂L2 shows higher intensity than EuL1. For both Eu complexes, energy level of triplet excited-state BP (³BP*) is only 3 kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺. The ⁵D₂ state formed by a triplet-energy transfer (TET) from ³BP* is therefore deactivated by a back energy transfer (BET) to the ground-state BP, resulting in low luminescence intensity of EuL1. In contrast, within Eu₂L2, TET from ³BP* to ⁵D₀ state of two Eu³⁺ ions is accelerated, thus leading to higher luminescence intensity. Another notable feature of Eu₂L2 is the luminescence quantum yield independent of its concentration. In contrast, for EuL1 system, an intermolecular BET occurs from ⁵D₂ state of Eu³⁺ to the ground-state BP conjugated to another EuL1 complex, resulting in a yield decrease with the concentration increase.     

Spectroscopic and thermodynamic features of conical bubble luminescence

The influence on luminescence from conical bubble collapse (CBL) with varying Ar gas content while perturbing the liquid 1,2-Propanediol (PD) has been investigated. The temporal, spatial, and spectral features were analysed with regards to the dynamics of collapse and liquid degradation. Sulphuric acid and sodium chloride were added to disturb the liquid. The following three cases were studied: PD/Ar, (I), (PD + H₂SO₄)/Ar, (II), and (PD + H₂SO₄ + NaCl)/Ar, (III). The intensities of those cases decrease as III > II > I. Temporally, single and multiple light emissions were found to occur. The pulse shape exhibited a large variety of profiles with a main maximum and up to two local maxima around the main maximum. These local maxima resembled those generated by laser cavitation. Spatially, no radial symmetry was detected in the light emissions. Spectrally, the Swan, CH and CN lines were observed at low volumes of gas and driving pressure. The OH radical and OH-Ar bands, as well as the Na and K lines, consistently appeared superimposed on an underlying continuum that almost disappeared in (III). The Na line was observed with two satellite diffuse bands representing Na-Ar complexes in (I) and (II), whereas in (III), only the line of sodium could be seen. Weak and diffuse emission lines from the Ar atom in the near-IR region were observed in (I) and (II).The proposed mechanism of bright CBL was based on the energy transfer from electron-excited homolytic cleavage products to the chromophore molecules generated during the collapse-rebound time line (∼8200 K and ∼1 ms of collapse time from model), which had accumulated inside the liquid and remained on the walls of cavity during the repetition of the collapse. A general mechanism for the bright CBL is broached.     

Nature of electric and magnetic dipoles gleaned from the Poynting theorem and the Lorentz force law of classical electrodynamics

Starting with the most general form of Maxwell's macroscopic equations in which the free charge and free current densities, ρ_free and J_free, as well as the densities of polarization and magnetization, P and M, are arbitrary functions of space and time, we compare and contrast two versions of the Poynting vector, namely, S = μ_o^− 1E × B and S = E × H. Here E is the electric field, H is the magnetic field, B is the magnetic induction, and μ_o is the permeability of free space. We argue that the identification of one or the other of these Poynting vectors with the rate of flow of electromagnetic energy is intimately tied to the nature of magnetic dipoles and the way in which these dipoles exchange energy with the electromagnetic field. In addition, the manifest nature of both electric and magnetic dipoles in their interactions with the electromagnetic field has consequences for the Lorentz law of force. If the conventional identification of magnetic dipoles with Amperian current loops is extended beyond Maxwell's macroscopic equations to the domain where energy, force, torque, momentum, and angular momentum are active participants, it will be shown that “hidden energy” and “hidden momentum” become inescapable consequences of such identification with Amperian current loops. Hidden energy and hidden momentum can be avoided, however, if we adopt S = E × H as the true Poynting vector, and also accept a generalized version of the Lorentz force law. We conclude that the identification of magnetic dipoles with Amperian current loops, while certainly acceptable within the confines of Maxwell's macroscopic equations, is inadequate and leads to complications when considering energy, force, torque, momentum, and angular momentum in electromagnetic systems that involve the interaction of fields and matter.     

Synthesis and optical properties of novel pyrido[1,2-a]benzimidazole-containing 1,3,4-oxadiazole derivatives

A series of novel substituted 1,3,4-oxadiazole derivatives containing pyrido[1,2-a]benzimidazole moiety were synthesized and characterized using FTIR, ¹H NMR, ¹³C NMR, and HRMS. An efficient tandem reaction was employed as a key step in constructing the pyrido[1,2-a]benzimidazole moiety under very mild condition. The structure of compound 4a was established by X-ray crystallography. The UV-vis absorption and fluorescence spectral characteristics of these compounds were investigated in several solvents. Compounds 4a-i display similar absorptions, with absorption peaks ranging from 330 to 339 nm in acetonitrile, while the absorption maxima of compound 4j bearing a diphenylamino group on the benzene ring is red-shifted distinctly to 377 nm due to the strong electron-donating property of its substituent and extended π-conjugated system. All these target heterocyclic compounds present blue-green emissions (461-487 nm) in dilute solutions and show high quantum yields of fluorescence (Ф_PL=0.65−0.99) in dichloromethane.     

Second-order optical nonlinearities from χ gratings induced by holographic all-optical poling

The paper presents the second-order optical nonlinearities from χ⁽²⁾ gratings induced by holographic all-optical poling for azobenzene polymer. Second harmonic (SH) signal along the directions with two different vectors was measured. One is strong SH signal diffracted in the same direction as 2ω writing beam with wave vector k_2ω and the other is weak SH signal diffracted in the direction of wave vector of 4k_ω - k_2ω + Δk where k_ω is wave vector of ω beam and Δk is the wave vector mismatch whose vector is parallel to k_ω. The latter signal was used as a tool to monitor the formation of holographic χ⁽²⁾ gratings in real-time because it has off-axis wave vector different from both k_ω and k_2ω. The increase of 2ω intensity on poling process led to the large increase of second-order optical nonlinearity. The real-time monitoring showed that it also gave the large relaxation of second-order optical nonlinearity on poling process. The increase of 2ω (532 nm) energy enhanced the increase of local heating, which led to easier alignment of azobenzene chromophore and also larger relaxation of aligned chromophore.     

The synthesis and photophysical properties of novel cationic tetra pyridiloxy substituted aluminium, silicon and titanium phthalocyanines in water

This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor^® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.     

Organic radical molecular solids based on [(TCNQ)n] (n=1 or 2): Syntheses, crystal structures, magnetic properties and DFT analyses

Four molecular solids consisting of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical and benzylpyridinium or benzylquinolinium derivatives with molar ratios of 1:1 (1-3) and 2:1 (4) have been prepared and characterized. In the crystals of 1 and 3, TCNQ⁻ monoanions and the corresponding cations form segregated stacks, which are regular in 1 but irregular in 3. Instead of segregated stacks, TCNQ⁻ monoanions in 2 form isolated π-dimers. In the crystals of 4, two crystallographic independent TCNQ species possess almost equal fractional negative charge (ca. −0.5). Two types of TCNQ species form a tetrad, these tetrads make a TCNQ stack with the pattern …BAAB…BAAB… along the crystallographic a-b direction. The magnetisms for 1-4 can be simply explained by the formation of singlet spin state. A broken symmetry approach in a density functional theory framework at the ub3lyp/6-31 g level was used to calculate the magnetic exchange constants in 1-4. The results qualitatively demonstrate the observed magnetic properties.     

Photophysical characteristics of 4,4′-bis(N-carbazolyl)tolan derivatives and their application in organic light emitting diodes

4,4′-bis(N-carbazolyl)tolan (BCT) and 4,4′-bis[N-(3,6-di-t-butyl)carbazolyl]tolan (BCT-t-Bu) were synthesized as π-expanded analogs of 4,4′-bis(N-carbazolyl)biphenyl. Their photophysical characteristics both in solution and films were thoroughly investigated. Interestingly, the phosphorescence spectrum of BCT was significantly medium-dependent, and the emission maximum was red-shifted by 131 nm from 489 nm in solution at 77 K to 620 nm in a deposited film at 5 K, suggesting the presence of strong intermolecular interactions in the film. BCT and BCT-t-Bu were found to be useful as host materials for fluorescence-based organic light emitting diodes (OLEDs). However, their low triplet energy levels in films negated their potential to act as hosts in phosphorescence-based OLEDs.     

Sensitized luminescence of Eu and Tb macrocyclic complexes bearing benzophenone antennae

Sensitized luminescence behavior of lanthanide (Ln=Eu³⁺, Tb³⁺) macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) complexes bearing one or four benzophenone (BP) moieties as antenna (LnL1 and LnL4) has been studied in water. Despite higher molar extinction coefficient of EuL4 owing to four antennae, it shows only one-thirtieth the luminescence intensity of EuL1. Energy level of triplet excited-state of BP antenna (E_T) is only a few kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺, thus promoting a back energy transfer (BET) from ⁵D₂ of Eu³⁺ to ground-state BP antennae. On EuL4 bearing four antennae, BET occurs more rapidly than that on EuL1, thus exhibiting much weaker luminescence. For Tb complexes, the energy gap between E_T of BP antenna and ⁵D₄ excited state of Tb³⁺ is large enough (>13 kJ mol⁻¹), such that practically no BET occurs. The luminescence intensity of TbL4 is, however, lower (two-third) than that of TbL1. Time-resolved luminescence measurement reveals that hydration number of Tb³⁺ within TbL4 is twice that within TbL1. This is because the structural distortion of ligands on TbL4, caused by an intramolecular dipole-dipole interaction among the BP antennae, allows coordination of higher number of H₂O molecules to Tb³⁺, thus leading to a strong Tb luminescence quenching via O-H oscillators.     

Synthesis, characterization and optical limiting effect of nickel complexes of multi-sulfur 1,2-dithiolene

Three nickel complexes with a new multi-sulfur 1,2-dithiolene ligand, (n-Bu₄N)[Ni(cddt)₂] 1, (Ph₄P)[Ni(cddt)₂] 2 and [Ni(cddt)₂] 3 (cddt=4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3-dithiolate), have been synthesized and characterized by electrochemical measurements, IR, EPR and UV-Vis-NIR spectroscopies. The crystal structure of complex 2 is determined. Their optical nonlinearities are measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm and all exhibit NLO absorptive abilities. Complexes 1 and 2 both exhibit effective self-defocusing performance (n₂=−5.81×10⁻¹⁰ esu for 1 and −4.51×10⁻¹⁰ esu for 2). The optical limiting (OL) effects were observed with nanosecond and picosecond laser pulses. The OL capability of complex 3 is superior to C₆₀ at the same experimental condition in ns measurements.     

High light electroluminescence of novel Cu(I) complexes

Three novel Cu(I) complexes, [CuDPEphos(NN)]BF₄, where NN=1-(4-5′-phenyl-1,3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (OXD-Pybm; L1) (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzimidazole (Carl-Pybm; L2) (2), and 1-H-2-pyridinylbenzimidazole (HPybm; L3) (3), were synthesized. The photoluminescent (PL) properties of 1-3 and the electroluminescent (EL) properties of complexes 1 and 2 were systematically studied. The maximum brightness of 2-based devices was 8669 cd/m², which should be the best among the reported Cu(I) complexes-based devices.