Linear and tri-branched copolymers for two-photon absorption and two-photon fluorescent materials

The one- and two-photon properties of linear (M2) and tri-branched (M3) copolymers with triphenylamine and cyano groups in the main chain were experimentally investigated. Open-aperture z-scan experiments were performed with 1 kHz, 120 fs, and 800 nm Ti:sapphire laser pulses to measure the two-photon absorption cross sections. The two-photon cross sections of M2 and M3 were determined to be 0.304 and 1.441×10⁻²⁰ cm⁴/Gw per repeating unit, respectively. In a CHCl₃ solution, M2 and M3 emit strong frequency up-converted fluorescence under the excitation of 120 fs pulses at 800 nm with the peaks located at 561 and 542 nm.     

Nonlinear optical transmission of silk/green fluorescent protein (GFP) films

In this initial work, we demonstrate a technique for preparing thin (10-20 μm) films of silk doped with green fluorescent protein (GFP) by casting/annealing at 20 °C and describe the resulting film characteristics. Notably, the GFP molecules maintain their nonlinear optical properties as evidenced by two-photon fluorescence microscopy and two-photon absorption measurements using near-infrared femtosecond pulses. The fractional transmission of focused near-infrared pulses of 775 nm wavelength, 140 fs pulsewidth was observed to decrease as the incident pulse energy is increased and/or the incident spot size is decreased, indicating that nonlinear absorption is taking place. Visible damage from the pulses is observed in a ∼10 μm film at the highest peak incident fluences, which were in the range of 0.1-0.2 J/cm². Variations in thickness, morphology and GFP concentration of the films make precise specification of the two-photon absorption coefficient difficult. Since these films have potential applications in photonics, we suggest techniques for improving these properties in future generations of films. The suggestions present opportunities for future work.     

The photophysics and two-photon absorption of a series of quadrupolar and tribranched molecules: The role of the edge substituent

A series of quadrupolar and tribranched molecules were synthesized in order to examine the role of the edge substituents on their photophysical and two-photon absorption properties. Two-photon absorption cross sections, δ, of the molecules were determined in THF solution using a two-photon excited fluorescence technique with femtosecond pulsed excitation. The quadrupolar molecules contained a fluorene or alcoxy-substituted phenylene central core together with various electron accepting edge substituents such as pyridine, terpyridine, phthalimide and naphthalimide. The tribranched molecules contained triphenylamine at the center and terpyridine or phthalimide substituents at the periphery. It was found that edge phthalimide substituent favour high δ values. δ Values as high as 1660 GM and 1500 GM were obtained from the phthalimide-fluorene-phthalimide and phthalimide-phenylene-phthalimide molecules, respectively; in the case of the tribranched molecule with a phthalimide substituent, a δ-value of 1200 GM was found.     

Synthesis and properties of polyacetylenes carrying N-phenylcarbazole and triphenylamine moieties

Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(1) and poly(2) with high number-average molecular weights (15?500-974?000) were obtained in good yields (77-97%), when [(nbd)RhCl]₂-Et₃N (nbd = norbornadiene) was used as a catalyst. The polymers exhibited UV-vis absorption peaks derived from the Cz and TPA moieties at 250-350 nm and polyacetylene backbone above 350 nm. The UV-vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV-vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(1). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl]₂-Et₃N were larger than those of the Rh⁺(nbd)[η⁶-C₆H₅B⁻(C₆H₅)₃]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350-420 °C under air, indicating the high thermal stability.     

Copolymers containing pendant styryltriphenylamine and carbazole groups: Synthesis, optical, electrochemical properties and its blend with Ir(ppy)3

A series of vinyl copolymers (PVKST12-PVKST91) and homoploymer PVST containing pendant hole-transporting 4-(4-oxystyryl)triphenylamine (12-100 mol%) and carbazole chromophores were synthesized by radical copolymerization and employed as host for Ir(ppy)₃ phosphor to tune emission color. They were characterized using the ¹H NMR, FT-IR, absorption and photoluminescence spectra, elemental analysis, GPC, cyclic voltammetric and thermal analysis (DSC, TGA). Their weight-average molecular weights (M_w) and decomposition temperatures (T_d) were 1.46-5.68 × 10⁴ and 356-399 °C, respectively. The HOMO levels of PVKST12-PVKST91 and PVST, estimated from the onset oxidation potentials in cyclic voltammograms, were −5.40 to −5.14 eV, which are much higher than −5.8 eV of the conventional host poly(9-vinylcarbazole) (PVK) owing to high hole-affinity of the 4-(4-oxystyryl)triphenylamine groups. Therefore, copolymers PVKST are effective in reducing hole-injection barrier between the PEDOT:PSS and emitting layer. Electroluminescent devices [ITO/PEDOT:PSS/PVKST:Ir(ppy)₃:PBD/BCP/Ca/Al] using the hole-transporting PVKST as host were fabricated to tune the emission color. Their EL spectra showed a major emission at 515 nm and a minor peak at 435 nm attributed to Ir(ppy)₃ and 4-(4-oxystyryl)triphenylamine, respectively. The C.I.E. 1931 coordinates shift from (0.29, 0.61) for PVK to (0.33, 0.42) for PVST with an increase in 4-(4-oxystyryl)triphenylamine content.     

The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties

Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D_2d (Cu^I, Ag^I, Zn^II) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis[4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β_1.91 in the range of 211-340 × 10⁻³⁰ esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections.     

The synthesis and two-photon excited fluorescence properties of novel branched fluorene derivatives

Two novel, V-shaped fluorene derivatives branched from triphenylamine and their linear analogue were synthesized via Cu-mediated Ullmann condensation and subsequent Pd-catalyzed Heck coupling reaction. Their two-photon excited fluorescence properties as well as their linear absorption and single-photon excited fluorescence properties were examined. When excited at 730 nm by a Ti:sapphire femtosecond laser, the compounds exhibited strong two-photon excited blue fluorescence. The two-photon excited fluorescence cross-sections of V-shaped derivatives in toluene at 730 nm were 506 GM in the case of N, N-bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-aniline) and 397 GM for N, N-Bis{7-[4′-(N, N-diphenylamino)styryl]-9,9-diethyl-9H-fluorene-2-yl}-4-acetyl-aniline), respectively.     

Green and red upconversion luminescence of Er-doped K0.5Na0.5NbO3 ceramics

Er³⁺ doped K_0.5Na_0.5NbO₃ (KNN) lead-free piezoelectric ceramics were synthesized by the solid-state reaction method. The upconversion emission properties of Er³⁺ doped KNN ceramics were investigated as a function of Er³⁺ concentration and incident pumping power intensity. Bright green (~555 nm) and red (670 nm) upconversion emission bands were obtained under 980 nm excitation at room temperature, which are attributed to (²H_11/2, ⁴S_3/2)→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions, respectively. The upconversion emission intensity can be adjusted by changing Er³⁺ concentration, and the mechanism of upconversion processes involve not only a two-photon absorption but also a three-photon absorption. In addition to the admirable intrinsic piezoelectric properties of KNN, this kind of material may have potential application as a multifunctional device by integrating its upconversion and piezoelectric property.     

High glass transition and thermal stability of new pyridine-containing polyimides: Effect of protonation on fluorescence

A new diamine monomer containing heterocyclic pyridine and triphenylamine groups, 4-(4,4′-diaminotriphenylamine)-2,6-bis(4-methylphenyl)pyridine (4), was synthesized by Chichibabin and nucleophilic fluoro-displacement reactions. The diamine was used to prepare a series of novel polyimides via polycondensation with various aromatic tetracarboxylic dianhydrides in N-methyl-2-pyrrolidinone. The polyimide 4a derived from the diamine 4 with 4,4′-hexafluoroisopropylidenediphthalic anhydride and having high T_g (313 °C), mechanical, and thermal properties was soluble in various organic solvents, such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, chloroform, tetrahydrofuran, at room temperature. The polyimide (4a) could be cast into a self-standing film from DMAc solution and was thermally converted into tough and flexible film. The film had high tensile modulus of 2.2 GPa and exhibited excellent thermal stability in both nitrogen and air (T_d¹⁰ > 550 °C). The pristine polymer exhibited the UV-vis absorption bands in the region 240-400 nm and protonated polymer exhibited absorption in the region 390-500 nm. The protonated polymer possessed strong orange fluorescence (around 600 nm) in THF solution after protonation with acids as excited at 438 nm. The fluorescent intensity was influenced by the acid concentrations and the chemical structure of conjugated bases. The fluorescent intensity at 600 nm increased as acid concentration from a lower to a moderate concentration and decreased at higher concentrations.     

Time-resolved spectroscopy of infrared active vibrations in 2,5-dioctyloxy poly(phenylene vinylene) films

We report on picosecond time resolved spectroscopy of photogenerated infrared active vibrations in thin films of 2,5-dioctyloxy poly(phenylene vinylene). We excited the films by ?4 ps long pulses of 565 nm laser light with 2×10¹³ photons/cm² per pulse and repetition rate of 76 MHz. We then followed the temporal evolution of the infrared active vibrational (IRAV) spectrum using a subsequent, variably delayed, weak tunable IR probe pulses of similar temporal duration. Under these conditions, we show clear spectroscopic evidence for photogenerated infrared active vibrations at times which are shorter than our temporal resolution (<4 ps). We suggest that the transient IRAV absorption is due to secondary polarons formation following exciton dissociation.     

Poly(thienylene-benzothiadiazole-thienylene-vinylene): A narrow bandgap polymer with broad absorption from visible to infrared region

Poly(thienylene-benzothiadiazole-thienylene-vinylene) (PTBTV) has been synthesized by Pd-catalyzed Stille-coupling method. The polymer shows broad absorption from visible to infrared region. The maximum absorption of PTBTV in solution and film state is at 600 nm and 614 nm, respectively. The absorption edge of PTBTV film is at 813 nm, indicating a narrow bandgap of 1.50 eV. The HOMO and LUMO energy levels of PTBTV are −4.99 eV and −3.49 eV, respectively. Polymer solar cell based on the blend of PTBTV as donor and [70] PCBM as acceptor was fabricated, the power conversion efficiency of the device is 0.51% under the illumination of AM1.5, 100 mW/cm².     

Synthesis and Self-Organization of Fluorene-Conjugated Bisimidazolylporphyrin and Its Optical Properties

A conjugated-bisimidazolylporphyrin bridged by bis(ethynylfluorene) was synthesized and organized into linear polymer through self-coordination having mean molecular weights, M_w and M_n, of ~2.1 × 10⁵ Da and ~1.6 × 10⁵ Da, respectively. A large two-photon absorption cross section value of 3.4 × 10⁵ GM (per dimer unit) was observed. This value was comparable to that of the previously reported self-assembled linear polymer consisting of butadiyne-bridged imidazolylporphyrins. The two-photon absorption properties could be controlled by tuning the wavelength and absorption intensity of the one-photon absorption.     

Two-photon absorption dyes with thiophene as π electron bridge: Synthesis, photophysical properties and optical data storage

Four novel dyes are prepared by thiophene as π bridge between carbazole central core and other terminal groups by Suzuki and Heck coupling reactions. These dyes are fully characterized by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. Linear absorption, single- and two-photon excited fluorescence in various solvents are experimentally investigated. The calculated two-photon absorption cross sections of 9-Hexyl-3,6-di((5-phenyl)-2-thienyl)carbazole (1), 9-Hexyl-3,6-di((5-thienyl)-2-thienyl)carbazole (2), 9-Hexyl-3,6-di((5-p-vinylpyridyl)-2-thienyl)-carbazole (3) and 9-Hexyl-3,6-di-((5-o-vinylpyridyl)-2-thienyl)carbazole (4) for the lowest excited state are 537.84, 550.76, 1292.95 and 1340.40 × 10⁻⁵⁰ cm⁴ s photon⁻¹, respectively. Calculated and experimental data have shown that thiophene as π electron bridge improves the two-photon absorption cross sections greatly. Two-photon optical data recording experiments have been carried out at 820 nm laser radiation.     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光。化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM。这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料。     

The influence of tetrakis-ethylhexyloxy groups substituted in PPV derivative for PLEDs

New electroluminescent polymer with tetrakis-alkoxy group, poly[2,3,5,6-tetrakis(2-ethylhexyloxy)-1,4-phenylenevinylene] (TEH-PPV), has been synthesized by the Gilch polymerization. In solid film state, the TEH-PPV exhibits absorption spectra with maximum peaks at 451 nm, and PL spectrum at 505-545 nm. As compared to MEH-PPV, TEH-PPV with tetrakis-ethylhexyloxy groups in phenylene unit can get shorter conjugation length, and had more blue shifted absorption and emission peaks due to steric hindrance, in spite of increasing the number of alkoxy substituents which may increase the effective conjugation length caused by the electron-donating effect. The polymer LEDs (ITO/PEDOT/polymer/Al) of TEH-PPV showed emission with maximum peaks at around 505-590 nm. Tetrakis-ethylhexyloxy groups induced very typical vibronically structured band in solid film state, since the conjugated backbone is twisted by steric hindrance. And they can enhance the internal efficiency of the conjugated polymer as emissive layer in PLED because of the restraint of inter-chain interaction by the avoidance of close packing to give decent device performance.     

Novel electrochromic aromatic poly(amine-amide-imide)s with pendent triphenylamine structures

Three new aromatic poly(amine-amide-imide)s (PAAIs) having pendent triphenylamine units were prepared from the phosphorylation polyamidation reactions of a newly synthesized diamine, N,N-bis(4-aminophenyl)-N′,N′-diphenyl-1,4-phenylenediamine, with three imide ring-preformed dicarboxylic acids. These PAAIs had inherent viscosities of 0.54-0.86 dL/g, and they were amorphous and readily soluble in many organic solvents and could be solution cast into transparent, tough, and flexible films with good mechanical properties. They displayed relatively high glass-transition temperatures (279-287 °C) and good thermal stability, with 10% weight-loss temperatures in excess of 522 °C in nitrogen and char yields at 800 °C in nitrogen higher than 67%. The solutions of polymers in NMP exhibited strong UV-vis absorption bands with a maximum around 315 nm. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the PAAIs prepared by casting polymer solution onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.67 and 1.08 V vs. Ag/AgCl in acetonitrile solution. All the PAAIs revealed very stable electrochromic characteristics, changing color from original pale brownish to green, and then to blue at 0.67 and 1.08 V, respectively.     

Luminescent Nd doped silicone-urea copolymers

A simple method for the preparation of rare earth ion-doped polymers, which display luminescence, is reported. For this purpose silicone-urea copolymers were doped with Nd(NO₃)₃·6H₂O. Various structural and physicochemical properties of the resultant materials were investigated. FTIR studies indicated strong interaction of Nd³⁺ ions with urea groups, but no interaction with siloxane backbone, which is expected. Absorption measurements in the visible and near infrared region were performed and the radiative decay rates and branching ratios for the meta-stable ⁴F_3/2 level were determined by using Judd-Ofelt theory. The samples were also excited at 800 nm and emission spectra were observed in the near infrared at 905, 1059, and 1331 nm. In Nd³⁺ doped silicone-urea systems the highest emission cross section at 1059 nm was determined to be 60.7×10⁻²¹ cm². Spectroscopic parameters determined in this study suggest that Nd³⁺ doped silicone-urea copolymers are promising candidates for the development of fiber lasers or amplifiers near 1.06 and 1.3 μm.     

Novel conjugated alternating copolymer based on 2,7-carbazole and 2,1,3-benzoselenadiazole

A novel conjugated alternating copolymer (PCzDBSe) based on N-9′-heptadecanyl-2,7-carbazole and 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) was synthesized by Suzuki polycondensation. The polymer reveals excellent thermal stabilities with the decomposition temperature (5% weight loss) of 390 °C and the glass-transition temperature of 140 °C. The absorption peaks of the polymer are located at 412 and 626 nm, respectively, while the absorption onset is extended to 716 nm, which is 56 nm red-shifted as compared with its analogue, poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT). The HOMO and LUMO levels of the polymer were estimated to be −5.28 and −3.55 eV, respectively, with an optical bandgap of 1.73 eV. The hole mobility of PCzDBSe as deduced from a solution-processed organic field effect transistor (OFET) was found to be 3.9 × 10⁻⁴ cm² V⁻¹ s⁻¹. Polymer solar cells (PSCs) based on the blends of PCzDBSe and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) with a weight ratio of 1:4 were fabricated. Under AM 1.5 (AM, air mass), 100 mW cm⁻² illumination, the devices were found to have an open-circuit (V_oc) of 0.75 V, a short-circuit current density (J_sc) of 7.23 mA cm⁻², a fill factor (FF) of 45% and a power conversion efficiency (PCE) of 2.58%. The primary results indicate that 5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzoselenadiazole) is a promising unit for low bandgap polymer for polymer solar cells.     

Wavelength and temperature dependences of the absorption and scattering cross sections of soot

We have inferred the wavelength and temperature dependence of the absorption and scattering cross sections of mature soot in an ethylene flame from laser-induced incandescence (LII) and transmittance measurements at 532 and 1064 nm. The LII measurements indicate that the emissivity of soot in a flame deviates from the expected 1/λ dependence. Combining the LII results with transmittance measurements yields single-scattering albedos of 0.058-0.077 at 1064 nm and 0.22-0.29 at 532 nm and values of F(m)/E(m) of 2.2-2.9 at 532 nm and 2.4-3.3 at 1064 nm. These values confirm that scattering must be taken into account when interpreting extinction data at these wavelengths. Our results also indicate increases in the absorption cross section and decreases in the scattering cross section with increasing fluence at low fluences. The increase in absorption cross section is consistent with increases in primary particle size with increasing particle temperature during laser heating. The decrease in scattering cross section could be attributable to an increase in the radius of gyration or a decrease in the fractal dimension of the aggregate with increasing temperature. Alternatively these trends might be the result of changes to the optical properties of the particles with increasing temperature.     

Sol–gel synthesis of red-emitting LiEuW2O8 powder as a near-ultraviolet convertible phosphor

LiEuW₂O₈ phosphor with the optical function of color conversion from near-UV to red wavelength was prepared by sol–gel method using inorganic salts as a starting material. Viscous mixing sol was prefired at 300 °C for 120 min in air and then white precursor was finally annealed at 800 °C for 240 min in Ar. Structural and photoluminescent properties of the sample were analyzed by an X-ray diffraction analysis, field emission-scanning electron microscope and a fluorescent spectrophotometer. The main emission peak is ⁵D₀ → ⁷F₂ transitions of Eu³⁺ at 615 nm, other transitions from the ⁵D₀ → ⁷F₁, ⁵D₀ → ⁷F₃ and ⁵D₀ → ⁷F₄ located at 570–700 nm range are weak. The characteristic emission of WO₄²⁻ in LiEuW₂O₈ is quenched absolutely and only red-light emission of Eu³⁺ appears.