Pyrromethene Research Articles

Enhanced quantum efficiency of dicyano BODIPYs over difluoro BODIPYs: A DFT approach

The modified BODIPY (pyrromethene) dyes with cyano (-CN), substituting usual fluorine (-F), at the 4-position may give enhanced photochemical stability and quantum yield of fluorescence (QYF) when compared to the corresponding fluoro derivative. We have investigated and discussed comparatively the structural parameters of the ground (S0) and excited (S1) state geometries of a few widely used BODIPY dyes, both 4-cyano and 4-fluoro pyrromethene (PM), through DFT and TD-DFT studies and established the reasons for improved QYF of the cyano derivatives. The electrophilicity index indicates the stability of the excited geometry of the cyanated BODIPY and the calculated transition dipole moments reveal a longer lifetime of the excited state (S1) for the cyano BODIPY. The higher singlet and triplet gap in cyanated BODIPY accounts for higher QYF due to restricted transition from singlet to triplet state. This suggests that a population inversion, crucial for laser action, is easier to build up for cyano derivative than for the commonly used fluoro analogue while other gain/loss parameters of the PM dye lasers remain similar. Hence, 4-cyano derivatives of the PM dyes may be useful for more efficient lasing applications. The non-linear optical properties of the PM dyes are also investigated.

Sustainable Development in Dye Waste Managemen : A Comparative Study on the Effectiveness of Adsorption and γ-Radiolysis

Pyrromethene 567 (PM567), a BODIPY class of dye; is widely used in medicine, chemistry, material science, and high-power dye lasers. During its use, PM567 dye waste is generated in ethanol solvent which needs to be treated before its disposal. In our study, we -radiolysis, an advanced oxidation process (AOP), and adsorption, a simple and easy option. Interestingly, -radiolysis were not efficient for dye effluent treatment in organic solvents. This inefficiency was attributed to competing reactions leading to the scavenging of dye-degrading radicals. -dose rate (3.5 kGy) feasible in the system; 62% is the maximum removal efficiency achieved by this method. For a comparison, we also investigated the adsorption efficiency of PM567 dye from ethanol solvent using commercially available adsorbents. Among these, powdered activated carbon (PAC) demonstrated the highest removal efficiency, reaching 95%, much higher than that of -radiolysis method. In line with the pursuit of sustainable development, we synthesized granular activated carbons (AC1, AC2, AC3) from coconut shells, a lignocellulosic biowaste. The characterization of these carbons revealed that AC3, with a higher iodine value and CCl4 activity, possessed a systematic pore structure (SEM analysis), a larger specific surface area (1708 m2 .g-1), and a higher micro-pore volume (0.61 cc.g-1). AC3 hence, emerged as the most effective adsorbent, achieving 95% efficiency comparable to PAC.

Manipulating random lasing correlations in doped liquid crystals.

Random lasers are highly configurable light sources that are promising for imaging and photonic integration. In this study, random lasing action was generated by optically pumping N-(4-methoxybenzylidene)-4-butylaniline (MBBA) liquid crystals infiltrated with gold nanoparticles and a laser dye (pyrromethene 597 (PM597)). By varying the pump energy near a lasing threshold, we show that it is possible to control intensity correlations between random lasing modes. The correlations in the system were phenomenologically characterized using the Levy statistics of the emission spectrum survival function. We also find that correlations and persistence of lasing action are correlated. These results demonstrate the possibility to dynamically control a key physical feature of random lasers, which may find applications in biomedical settings and network communications.

Efficient Fluorescence Utilization and Photon Density of States‐Driven Design of Liquid Crystal Lasers

AbstractLiquid‐crystal random lasers (LCRLs) represent a burgeoning field in soft‐matter photonics, holding promise for ushering in an era of ultrathin, versatile laser sources. Such lasers encompass a multitude of remarkable features, including wide‐band tunability, large coherence area and, in some cases, multidirectional emission. In this paper, an LCRL is developed by doping a laser dye, pyrromethene 597 (PM597), into cholesteric LC, but achieving a wide‐range wavelength‐controllable (560–720 nm) bandgap lasing through voltage control. Bandgap lasing intriguingly occurs in media with extremely low dye gain, which is mainly contributed by the extremely high photon density of states (DOS) at the edge of the LC bandgap. In addition, the utilization rate of the fluorescence spectrum (550–750 nm) of laser dye PM597 is as high as 80%. The multivariate linear regression model is used to characterize the inherent relationship between the lasing intensity emitted by LC and the photon DOS, fluorescence quantum yield, and internal scattering under specific pumping energy. This model shows the potential to predict the critical conditions of laser emission accurately and provides the capability to design and fabricate large‐scale multifunctional responsive photonic crystals using a simple fabrication procedure.

Design and construction of tunable solid-state dye laser pumped by flashlamp

Over the past six decades, dye laser technology has improved substantially. The usage of solid matrices containing laser dyes is becoming more and more popular as a viable substitute for the traditional liquid dye solutions. In this research, we designed and built a tunable solid dye laser device which consists of three main parts. (i) The active material producing the laser beam, which is a polymer rod [glycidyl methacrylate (GMA) polymer] doped with the laser dyes pyrromethene 597 (PM-597) or Nile blue (Nb-690). (ii) The pumping source is xenon linear flashlamp driven by a homemade power supply. (iii) Two broadband mirrors providing the optical feedback stable optical resonator. The properties of the gain medium and hence the laser emission characteristics were determined, and the results showed the efficiency of the homemade tunable solid dye laser device, that is suitable for a variety of applications.

Systematic photophysical investigation on pyrromethene 650 laser dye: Experimental and DFT approach

In the current study, we have chosen a highly fluorescent laser dye called pyrromethene 650 (PM-650) to investigate its photophysical properties using theoretical and experimental methods. We measured the absorption and emission spectra of PM-650 in polar protic and polar aprotic solvents at ambient temperature. Bathochromic and hypsochromic shifts were observed in the absorption and fluorescence spectra of the laser dye, confirming the presence of transitions between π → π* and n → π* states. We further estimated the ground and excited state dipole moments of PM-650 through experimental (solvatochromic correlations) and theoretical (ab initio) techniques, and compared the results. Interestingly, the PM-650 displayed an increased excited state dipole moment when contrasted with its ground state. Furthermore, using the B3LYP/6-311G++(d, p) approach, we estimated the natural bond orbital and molecular electrostatic potential map of PM-650 and discussed the results. Additionally, we theoretically determined the HOMO-LUMO energy band gap of PM-650 in different solvents with varying polarities, and found good agreement with the experimentally obtained values. To assess the reactivity and softness of PM-650, we calculated global chemical reactive descriptor values based on the theoretically estimated HOMO-LUMO. Our results suggest that PM-650 is highly reactive and possesses a soft nature.

Surfactant mediated suppression of aggregation and excited state ring puckering process in Pyrromethene 597-Application in water based dye laser

Water is being considered as an economical, safe and environmental friendly alternative solvent for dye lasers. However, the use of water in dye laser is restricted due to the formation of non-emissive aggregates of dye molecules. In the present study we have explored the possibility of the use of commercially available surfactant molecules for the water based laser of Pyrromethene 597 (PM597) dye, which has emerged as an alternative for more commonly used Rhodamine dyes in dye laser systems. Our studies show that in water, PM597 forms non-emissive aggregates which can be dissociated into monomeric dye molecules by adding common surfactants. Further, the high microviscosity in the micellar media retarded energy wasting ring puckering process in the excited state of the dye leading to the increase in its emission yield and excited state lifetime to a significant extent. It has been demonstrated that the emission yield and excited state lifetime in surfactant solution is relatively higher than in ethanol, the most commonly used organic solvent for dye lasers. Lasing action has been demonstrated in the aqueous solution of dye and lasing efficiency is found to be comparable to ethanol.

Titanium nitride random lasing induced by the plasmon resonance effect

Titanium nitride (TiN) is a promising plasmonic material with hard and abrasion-resistant specialities. In this study, a gain regime, namely, plasmon-enhanced random laser emission, is demonstrated in the Pyrromethene-597 (PM597) assisted by titanium nitride (TiN) film. For this, photoluminescence and random lasing are measured at different pumping energies from PM597/Silicon and PM597/TiN/Silicon samples. Enhanced lasing efficiency is observed in the PM597/TiN/silicon sample where a plasmon resonance is formed, which increases the energy transfer between TiN and PM597. Furthermore, the multiple scattering mediated by the TiN film also plays an important role for the lasing efficiency. It is worth mentioning that the random laser emission has a strong dependence on pump position. The study of the random laser from PM597/TiN/Silicon sample with film structure is aimed to obtain a good alternative (TiN) to replace noble metals at a lowest cost.

Coherent Random Lasing Realized in Polymer Vesicles

We have demonstrated the realization of a coherent vesicle random lasing (VRL) from the dye doped azobenzene polymer vesicles self-assembled in the tetrahydrofuran-water system, which contains a double-walled structure: a hydrophilic and hydrophobic part. The effect of the dye and azobenzene polymer concentration on the threshold of random laser has been researched. The threshold of random laser decreases with an increase in the concentration of the pyrromethene 597 (PM597) laser and azobenzene polymer. Moreover, the scattering of small size group vesicles is attributed to providing a loop to boost the coherent random laser through the Fourier transform analysis. Due to the vesicles having the similar structure with the cell, the generation of coherent random lasers from vesicles expand random lasers to the biomedicine filed.

Influence of fiber and MnCl_2 on mode and threshold of random lasing in random gain systems

A mode and threshold tunable random laser assisted by MnCl2 and fiber is investigated. This is constructed by doping MnCl2 with different concentrations and embedding fiber in the dye Pyrromethene-597(PM597)-doped negative liquid crystal (NLC) glass capillary samples. The excellent overlap of the absorption spectrum of MnCl2 with both the fluorescence and absorption spectra of dye PM597 provides the low threshold and tuning properties for the random lasing. The low-threshold and fewer-mode peculiarity of the random lasing for the systems with fiber is attributed to longer photon residence time provided by the fiber in the random gain-scattering systems. The simple and straightforward approach of random lasing control holds potential to enable optical device fabrication based on random lasers.

Coherent Random Lasing from Dye Aggregates in Polydimethylsiloxane Thin Films.

The coherent random laser (CRL) from dye-doped polydimethylsiloxane (PDMS) has been investigated in both nanoparticle-doped (NP-doped) thin films and pure dye thin films. Compared with the literature, the pump threshold is only 1.5 mJ/cm2 in the pure dye thin film with a low dye concentration. The spontaneously formed micro-/nanocrystals of Pyrromethene 597 (PM597) dye support both gain and random feedback in the bulk of the PDMS during the sample preparation. When the SiO2 NPs were doped, the pump threshold was reduced to 0.75 mJ/cm2. The threshold increased after the film was peeled off from glass, which indicates that the photon localization effect of the leaky-waveguide structure plays an important role in the reduction of the CRL threshold. By a change in the pump stripe length or the thickness of the film, the peak wavelength red-shifts 6.7 or 5.93 nm, respectively. The PM597 dye molecule solubility changes, and they spontaneously aggregate in the process of toluene volatilization; the PDMS cures, which is the reason for the formation of PM597 micro-/nanocrystals. This thin film random laser with a low dye concentration can be used in integrated optoelectronics and display imaging.

Tunable random polymer fiber laser

We have demonstrated the realization of on-line temperature-controlled random lasers (RLs) in the polyhedral oligomeric silsesquioxanes (POSS) nanoparticles (NPs) as well as Pyrromethene 597 (PM597) laser dye, Fe3O4/SiO2 NPs as well as PM597, and only PM597 doped polymer optical fibers (POFs), respectively. The RLs can be obtained from the gained POFs system caused by multiple scattering of emitted light. The refractive index of the fiber core materials can be easily tuned via temperature due to the polymer with large thermo-optic coefficient. Meanwhile, the scattering mean free path of core in the POFs, which is the key role for the emission wavelength of RLs, is strongly dependent on the matrix refractive index. Thus emission wavelength of RLs in the POF temperature can be controlled through changing the temperature. With the increasing the temperature, the RL emission wavelength has occurred red-shift effect for the POFs.

Random lasing assisted by CuSO_4 and Au nanoparticles in random gain systems

Random laser actions from a dye pyrromethene-597(PM597)-doped CuSO4 mixture infiltrated in glass capillaries are demonstrated. Discrete lasing modes are observed at the complete solid angle. Low threshold and variable emission wavelength of the random lasers are realized by adjusting the concentration of CuSO4 in the mixtures. With the exception of the multiple scattering of light caused by micro-crystals dispersed in the mixtures, another underlying physical mechanism for tuning random laser is closely related to energy transfer between the molecules of PM597 and CuSO4. Meanwhile, we also demonstrate the realization of a plasmonic random laser by doping Au nanoparticles (NPS) in the PM597-doped CuSO4 mixture. We find that the localized surface plasmon resonance of Au NPS lowers the threshold, increases the emission intensity and reduces the number of the lasing modes of the random lasers. Our results indicate that CuSO4 paves a new avenue towards designing low-cost photonic devices based on the random lasers.

Low-Threshold and High Intensity Random Lasing Enhanced by MnCl₂.

Energy transfer is known to have a significant influence on random lasers. However, the study about the effect of energy transfer between metallic salt and dye molecules on random lasers is still lacking at present. Here, we investigate random lasing actions in Pyrromethene-597 (PM597), PM597-doped MnCl2 (manganese (II) chloride), PM597-doped polymer-dispersed liquid crystal (PDLC) and PM597-doped PDLC with MnCl2 capillary systems. We find that random lasing of the systems with MnCl2 exhibits lower threshold, higher intensity, sharper peak and variable resonance wavelength in comparison with the systems without MnCl2. This behavior is closely related to the decrease of fluorescence quenching effect and the enhancement of local field induced by energy transfer between MnCl2 and PM597. Red-shift of wavelength is observed with increasing dosage concentration of MnCl2 in the PM597-doped PDLC with MnCl2 system. Through the analysis of single-shot emission spectra of PM597-doped PDLC without and with MnCl2 systems, the role of MnCl2 in the coupling of lasing modes is confirmed. Lengths of laser oscillation cavities of the PM597-doped PDLC without and with MnCl2 systems are calculated by a power Fourier transform (PFT) analysis of their emission spectra. It well accounts for the effect of MnCl2 on the variation of the oscillation cavity.

Random lasing based on rough dye-doped polymer thin film

In this work, a random laser action from rough dye film processed by surface rubbing with flannelette is reported. For the dye-doped polymer films with high surface roughness by surface rubbing, laser mode is stable, and threshold energy is found to be very low that is 333 μJ/cm2. By analyzing the random lasing spectrum using power Fourier transforms, an average resonator length was estimated as about 18.99 μm, which is 6.4 times larger than the film thickness. Furthermore, the influence of the concentration of Pyrromethene 597 (PM597) on the random laser was studied, and the results indicate that there is an optimum concentration for achieving the lowest threshold. Compared with glass groove structure with the dye doped film, the random laser based on the rough structure has reasonable time stability. This microstructure type random laser reported in this work is in low cost and easy to make compared with other laser structures of this category.

Tunable ultraviolet co-doped dye laser of Pyrromethene 597 and Rhodamine 610

The laser performance of Pyrromethene 597 (PM597) and Rhodamine 610 mixture is studied. A wide tuning range from 580 to 655 nm is achieved. The laser linewidth obtained is less than 0.1 nm. The highest conversion efficiency of 42.5% is obtained at 600 nm. Using a beta-BaB2O4 (BBO) crystal to frequency double the dye laser into ultraviolet (UV), a tuning range from 296 to 324 nm is obtained. The peak conversion efficiency from the dye laser to the UV laser is 9.7% and the highest UV laser output energy is 9.51 mJ at 301.25 nm. To the best of our knowledge, the tuning range and the conversion efficiency are the best under the same condition so far. All our results indicate that high laser performance can be achieved using a laser dyes’ mixture.

High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent.

Many pyrromethene (PM) dyes have been shown to outperform established rhodamine dyes in terms of laser efficiency in the green-yellow spectral region, but their rapid photochemical degradation in commonly used ethanol or methanol solvents continues to limit its use in high average power liquid dye lasers. A comparative study on narrowband laser efficiency and photostability of commercially available PM567 and PM597 dyes, using nonpolar n-heptane and 1,4-dioxane and polar ethanol solvents, was carried out by a constructed pulsed dye laser, pumped by the second harmonic (532nm) radiation of a Q-switched Nd:YAG laser. Interestingly, both nonpolar solvents showed a significantly higher laser photostability (∼100 times) as well as peak efficiency (∼5%) of these PM dyes in comparison to ethanol. The different photostability of the PM dyes was rationalized by determining their triplet-state spectra and capability to generate reactive singlet oxygen (O21) by energy transfer to dissolved oxygen in these solvents using pulse radiolysis. Heptane is identified as a promising solvent for these PM dyes for use in high average power dye lasers, pumped by copper vapor lasers or diode-pumped solid-state green lasers.

Structural and Spectroscopic Characterization of PM 597 Dye-Silica Core-Shell Nanoparticles

Nanostructured fluorescent pyrromethene (PM) doped-silica core-shell particles were successfully prepared by Stöber process. The average size of the particles was in the range of 10–20 nm measured by TEM micrograph. The atomic structure and morphology of PM 597/SiO2core/shell nanoparticles were studied by AFM and SEM, respectively. Absorption and emission spectra of the PM 597/SiO2core/shell nanoparticles under the UV irradiation were studied and not significantly influenced at the position of peaks. Finally, amplified spontaneous emission (ASE) and photobleaching of dye were examined and found no significant influence on the peaks of PM dye due to the formation of smaller sizes of PM 597/SiO2core/shell nanoparticles. The observed PM 597/SiO2core/shell nanoparticles were different in shapes with smaller size distribution and highly luminescent. Majority of nanoparticles were roughly spherical with many of them aggregated. The less photobleaching of dye core may be due to the protection of pumped energy by SiO2shell and restricts the leakage of dye.

Investigation of energy transfer from pyrromethene dye to cresyl violet 670 in ethanol

In this paper, radiative and nonradiative energy transfer from laser dye pyrromethene 567 (PM567) and pyrromethene 580 (PM580) as donors to cresyl violet 670 (CV670) as acceptor in ethanol are investigated by using the steady-state emission measurement and the second harmonic generation (532 nm, ∼ 13 ns) of a Q-switched Nd:YAG laser as the pumping source. The fluorescence intensity of the acceptor is improved due to the introduction of the donors, and the largest enhancement is obtained to be 128% in the PM567:CV670 dye mixture system. Energy transfer parameters, including the radiative and nonradiative energy transfer rate constants (KR and KNR), critical distance (R0), and half quenching concentration ([A]1/2) are investigated using the Stern—Volmer plots, and the acceptor concentration dependencies of radiative and nonradiative transfer efficiencies are also obtained. The values of KR for PM567:CV670 and PM580:CV670 systems are 2032.0×109 L·mol−1·s−1 and 2790.4×109 L·mol−1·s−1, respectively, and the values of corresponding KNR are 3.3 × 109 L·mol−1·s−1 and 4.2×109 L·mol−1·s−1, respectively. The results indicate that the dominant mechanism responsible for the energy transfer in the dye mixture systems is of the radiative type.

Vertical-cavity surface-emitting laser in the long-wavelength (700 nm) region in the visible by energy transfer between organic dyes

In this work, organic vertical-cavity surface-emitting lasers (VCSELs) with single-mode laser output in the long-wavelength region (~700 nm) of the visible were reported based on the energy transfer between dye pairs consisting of pyrromethene 597 (PM597) and rhodamine 700 (LD700). By co-doping PM597 into the polymeric hosts, the fluorescence intensity of LD700 was enhanced by 30-fold and the photophysical parameters of the donor–acceptor pairs were investigated, indicating the involvement of non-radiative resonance energy transfer processes between PM597 and LD700. Active distributed Bragg reflectors (DBR) were made by alternately spin-coating dye-doped polyvinylcarbazole and cellulose acetate thin films as the high and low refractive index layers, respectively. By sandwiching the active layer with 2 DBR mirrors, VCSEL emission at 698.9 nm in the biological first window (650–950 nm) was observed under the 532-nm laser pulses. The laser slope efficiency and threshold were also measured.