Nanoscale Organization of a Platinum(II) Acetylide Cholesteric Liquid Crystal Molecular Glass for Photonics Applications

The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans‐Pt(PEt₃)₂(C?C?C₆H₅?C?N)(C?C?C₆H₅?COO?Cholesterol), are described and designated as PE1‐CN‐Chol. Polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray scattering experiments show room temperature glassy/crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1‐CN‐Chol monolayer reveals self‐assembly at the solid?liquid interface with an array of two molecules arranged in pairs, oriented head‐to‐head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.     

Dye‐Doped Polyhedral Oligomeric Silsesquioxane (POSS)‐Modified Polymeric Matrices for Highly Efficient and Photostable Solid‐State Lasers

Here, the design, synthesis, and characterization of laser nanomaterials based on dye‐doped methyl methacrylate (MMA) crosslinked with octa(propyl‐methacrylate) polyhedral oligomeric silsesquioxane (8MMAPOSS) is reported in relation to their composition and structure. The influence of the silicon content on the laser action of the dye pyrromethene 567 (PM567) is analyzed in a systematic way by increasing the weight proportion of POSS from 1 to 50%. The influence of the inorganic network structure is studied by replacing the 8MMAPOSS comonomer by both the monofunctionalized heptaisobutyl‐methacryl‐POSS (1MMAPOSS), which defines the nanostructured linear network with the POSS cages appearing as pendant groups of the polymeric chains, and also by a new 8‐hydrogenated POSS incorporated as additive to the polymeric matrices. The new materials exhibit enhanced thermal, optical, and mechanical properties with respect to the pure organic polymers. The organization of the molecular units in these nanomaterials is studied through a structural analysis by solid‐state NMR. The domain size of the dispersed phase assures a homogeneous distribution of POSS into the polymer, thus, a continuous phase corresponding to the organic matrix incorporates these nanometer‐sized POSS crosslinkers at a molecular level, in agreement with the transparency of the samples. The silicon–oxygen core framework has to be covalently bonded into the polymer backbone instead of being a simple additive and both the silica content and crosslinked degree exhibit a critical influence on the laser action.     

Carboxylates versus Fluorines: Boosting the Emission Properties of Commercial BODIPYs in Liquid and Solid Media

A new and facile strategy for the development of photonic materials is presented that fufills the conditions of being efficient, stable, and tunable laser emitters over the visible region of spectrum, with the possibility of being easily processable and cost‐effective. This approach uses poly(methyl methacrylate) (PMMA) as a host for new dyes with improved efficiency and photostability synthesized. Using a simple protocol, fluorine atoms in the commercial (4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene) (F‐BODIPY) by carboxylate groups. The new O‐BODIPYs exhibit enhanced optical properties and laser behavior both in the liquid and solid phases compared to their commercial analogues. Lasing efficiencies up to 2.6 times higher than those recorded for the commercial dyes are registered with high photostabilities since the laser output remain at 80% of the initial value after 100 000 pump pulses in the same position of the sample at a repetition rate of 30 Hz; the corresponding commercial dye entirely loses its laser action after only 12 000 pump pulses. Distributed feedback laser emission is demonstrated with organic films incorporating new O‐BODIPYs deposited onto quartz substrates engraved with appropriated periodical structures. These dyes exhibit laser thresholds up to two times lower than those of the corresponding parent dyes with lasing intensities up to one order of magnitude higher.     

A Generalized System for Photo-Responsive Membrane Rupture in Polymersomes

Polymersomes are vesicles whose membranes are comprised of self-assembled block co-polymers. We recently showed that co-encapsulating conjugated multi-porphyrin dyes in a polymersome membrane with ferritin protein in the aqueous lumen confers photo-lability to the polymersome. In the present study, we illustrate that the photo-lability can be extended to vesicles containing dextran, an inert and inexpensive polysaccharide, as the luminal solute. Here we explore how structural features of the polymersome/porphyrin/dextran composite affect its photo-response. Increasing dextran molecular weight, decreasing block copolymer molecular weight, and altering fluorophore-membrane interactions results in increasing the photo-responsiveness of the polymersomes. Amphiphilic interactions of the luminal encapsulant with the membrane coupled with localized heat production in the hydrophobic bilayer likely cause differential thermal expansion in the membrane and the subsequent membrane rupture. This study suggests a general approach to impart photo-responsiveness to any biomimetic vesicle system without chemical modification, as well as a simple, bio-inert method for constructing photo-sensitive carriers for controlled release of encapsulants.     

Dramatic Structural Enhancement of Chirality in Photopatternable Nanocomposites of Chiral Poly(fluorene‐alt‐benzothiadiazole) (PFBT) in Achiral SU‐8 Photoresist

Materials with large optical activity at visible wavelengths are of great interest in photonics, particularly as one of the routes towards optical metamaterials. Here, dramatic structural enhancement of the optical activity of chiral poly(fluorene‐alt‐benzothiadiazole) (PFBT) when dispersed in SU‐8 to form a nanocomposite is reported. The supramolecular helical organization of PFBT chains in these optically clear nanocomposite films produces specific rotation at visible wavelengths that is 68 times that of a pure chiral PFBT film of the same optical absorbance. Photopatterning and development under standard conditions for SU‐8 leave behind a residual film of dispersed PFBT/SU‐8 aggregates in the nominally unexposed regions where the SU‐8 matrix is removed. After annealing, the patterned film exhibits specific rotation 58 times that of a pure chiral PFBT film of the same optical absorbance. Photopatterned and annealed films have a dissymmetry ratio as high as |g_abs| = 0.32. This dramatic enhancement is attributed to supramolecular helical organization of the aggregates within the nanocomposites and of the aggregates liberated from the SU‐8 matrix in the exposed regions.     

Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear Absorption of Light

The synthesis of trans‐di(arylalkynyl)diphosphine platinum(II) complexes bearing trialkoxysilane groups is described, as well as the preparation of siloxane‐based hybrid materials from organometallic chromophores through a modified sol–gel process. Glass materials prepared from trans‐[P(n–Bu)₃]₂Pt[(C≡C–p–C₆H₄–C≡C–p–C₆H₄–CH₂O(CO)NH(CH₂)₃Si(OC₂H₅)₃]₂ generally show spectral transmittance, absorption and luminescence similar to that of solutions reported in the literature. Measurements of optical power limiting for the hybrid glass are carried out, and show broadband nonlinear absorption throughout the whole visible wavelength range with clamping values in the range 0.2–7 µJ at 120 mM chromophore concentration. The sol–gel process using urethane‐propyltriethoxysilane‐functionalized chromophores as precursors appears to be a valid method for formation of robust silicate materials with grafted diarylethynyl Pt(II) complexes for OPL devices.     

高阶色散下饱和非线性负折射介质中的调制不稳定性

直接从负折射介质中包含高阶色散及饱和非线性效应的扩展非线性传输方程出发,采用线性稳定性分析法和德鲁德电磁模式,导出了调制不稳定性的色散关系和增益谱公式。考虑到今后的实验验证,以实际单位的形式计算了方程系数随归一化角频率的变化规律。再以实际单位的形式计算并讨论了增益谱随归一化角频率和归一化入射光强的变化关系。结果表明,当归一化角频率固定时,截止频率及峰值增益都随归一化入射光强的增加先增加后减少,归一化角频率不同,截止频率及峰值增益也不同,在靠近禁带处,增益谱远离零点。当归一化入射光强固定时,截止频率及峰值增益随归一化角频率的增加而增加,当归一化角频率增大到靠近禁带时,增益谱由紧挨零点变成远离零点。     

可溶性聚对苯乙炔衍生物非线性光学效应研究

以对甲氧基苯酚和溴代烷为原料,经过脱氯化氢反应合成了三种可溶性非对称烷氧基取代聚对苯乙炔 (PPV)衍生物,分别为聚(2 甲氧基 5 丁氧基)对苯乙炔(PMOBOPV)、聚[2 甲氧基 5 (3′ 甲基)丁氧基]对苯乙炔 (PMOMBOPV)和聚(2 甲氧基 5 辛氧基)对苯乙炔(PMOCOPV)。利用后向式简并四波混频(DFWM)研究了它们 的三阶非线性光学性质。结果表明PMOBOPV,PMOMBOPV和PMOCOPV的三阶非线性极化率(χ(3))分别为 3.14×10-10,5.96×10-10和3.71×10-10esu,相应的二阶分子超极化率(γ)分别为4.22×10-28,7.78×10-28和 5.00×10-28esu。分析了分子结构对聚对苯乙炔衍生物非线性光学性质的影响。采用分光光度计对三种材料的 光学禁带宽度(Eg)进行了测量,线性拟合的结果表明PMOBOPV,PMOMBOPV和PMOCOPV的Eg值分别为 2.08,2.03及2.05eV。     

4－甲氧基－3－甲基－4′－硝基二苯乙烯（MMONS）晶体生长与二阶非线性光学性质的研究

报道了ＭＭＯＮＳ的生长，研究了它的二阶非线性光学性能，为ＭＭＯＮＳ能实际应用提供了理论指导。     

Symmetric Versus Unsymmetric Platinum(II) Bis(aryleneethynylene)s with Distinct Electronic Structures for Optical Power Limiting/Optical Transparency Trade‐off Optimization

A new series of symmetric and unsymmetric Pt(II) bis(acetylide) complexes of the type D? C≡C? Pt(PBu₃)₂? C≡C? D (D? Pt? D), A? C≡C? Pt(PBu₃)₂? C≡C? A (A? Pt? A) and D? C≡C? Pt(PBu₃)₂? C≡C? A (D? Pt? A) (D, donor groups; A, acceptor groups) are synthesized, and show superior optical power limiting (OPL)/optical transparency trade‐offs. By tailoring the electronic properties of the aryleneethynylene group, distinct electronic structures for these metalated complexes can be obtained, which significantly affect their photophysical behavior and OPL properties for a nanosecond laser pulse at 532 nm. Electronic influence of the ligand type and the molecular symmetry of metal group on the optical transparency/nonlinearity optimization is thoroughly elucidated. Generally, aryleneethynylene ligands with π electron‐accepting nature will effectively enhance the harvesting efficiency of the triplet excited states. The ligand variation to the OPL strength of these Pt(II) compounds follows the order: D? Pt? D > D? Pt? A > A? Pt? A. These results could be attributed to the distinctive excited state character induced by their different electronic structures, on the basis of the data from both photophysical studies and theoretical calculations. All of the complexes show very good optical transparencies in the visible‐light region and exhibit excellent OPL responses with very impressive figure of merit σ_ex/σ_o values (up to 17), which remarkably outweigh those of state‐of‐the‐art reverse saturable absorption dyes such as C₆₀ and metallophthalocyanines with very poor transparencies. Their lower optical‐limiting thresholds (0.05 J cm^?2 at 92% linear transmittance) compared with that of the best materials (ca. 0.07 J cm^?2 for InPc and PbPc dyes) currently in use will render these highly transparent materials promising candidates for practical OPL devices for the protection of human eyes and other delicate electro‐optic sensors.     

Stabilization of Black Phosphorous Quantum Dots in PMMA Nanofiber Film and Broadband Nonlinear Optics and Ultrafast Photonics Application

The stabilization of black phosphorous quantum dots (BPQDs) for optical application under ambient conditions is highly challenging. Here, a facile approach is presented to substantially stabilize BPQDs by making a uniform BPQDs/polymethyl methacrylate (PMMA) composite nanofiber film via an electrospinning technique. As verified by femtosecond laser Z‐scan measurement, the BPQDs/PMMA composite nanofiber film that has been stored for three months exhibits almost the same nonlinear optical properties as the fresh BPQDs. Additionally, the BPQDs/PMMA composite nanofiber film demonstrates broadband nonlinear optical response ranging from the visible bandwidth (400 nm) to the mid‐IR bandwidth (at least 1930 nm). By employing the BPQDs/PMMA composite nanofiber film as an optical saturable absorber, an ultrashort pulse with the pulse duration of ≈1.07 ps centered at the wavelength of 1567.6 nm is generated in a mode‐locked fiber laser. These results suggest that the BPQDs/PMMA composite nanofiber film can combine the advantage of convenient integration and mitigation of the drawback of the easy oxidation of black phosphorous and pave the way for BP‐based practical optoelectronic devices.     

A New Series of Quadrupolar Type Two‐Photon Absorption Chromophores Bearing 11, 12‐Dibutoxydibenzo[a,c]‐phenazine Bridged Amines; Their Applications in Two‐Photon Fluorescence Imaging and Two‐Photon Photodynamic Therapy

A new series of quadrupolar type two‐photon absorption (2PA) chromophores 3 – 9 bearing a core arylamine‐[a,c]phenazine‐arylamine motif are synthesized in high yields. Palladium‐catalyzed Stille coupling and C? N coupling reactions are utilized to prepare target chromophores. Detailed characterization and systematic studies of these molecules, including absorption and fluorescence emission, are conducted. These compounds are found to exhibit very large 2PA cross section values, for example, ～7000 GM at 800 nm for 8 in toluene. Two‐photon‐induced fluorescence imaging is successfully demonstrated in vitro using compound‐ 8 ‐encapsulated silica nanoparticles with excellent bio‐compatibility. In combination with the capability of both one‐ and two‐photon singlet‐oxygen sensitizations, this nanocomposite demonstrates its promising potential in dual functionality toward two‐photon fluorescence imaging and two‐photon photodynamic therapy.