Strong Excited-state Absorption Research Articles

Solvent dependent trans → cis photoisomerization of N, N′-diacetylindigo studied by femtosecond time-resolved transient absorption spectroscopy

Solvent dependence of trans→cis photoisomerization of N,N′-diacetylindigo (DAI) was investigated by femtosecond transient absorption (TA) spectroscopy. A strong and sharp singlet excited state absorption band centered at 595nm was observed in the TA spectrum and the differential absorbance (ΔAbs) and the wavelength at the maximum of the band were periodically modulated by coherent vibrational wavepacket motions. However, even in the “reactive solvent”, ethyl acetate (EtAc), where the isomerization takes place, the formation of cis-DAI was unobservable in our experimental time window of 2ns which means that isomerization is occurring in a longer time scale. Preceding studies suggest that intermolecular hydrogen-bond (H-bond) with the solvent quenches the excited state and blocks the isomerization. Interestingly, we have observed that dimethylformamide (DMF) blocked the isomerization more efficiently than methanol. The excited state lifetime was shorter in DMF compared to EtAc solution suggesting that weak H-bonding with the formyl group of DMF is sufficient to prevent the slow trans→cis photoisomerization of DAI.

Optimization of ultrafast reverse saturable to saturable absorption transition in Ru dioxolene complex for all-optical logic applications

A detailed theoretical analysis of reverse saturable absorption (RSA) to saturable absorption (SA) transition has been presented in Ru complex [{Ru (bipy)2}2L][PF6], with picosecond laser pulses at 532 nm wavelength. Interestingly, it is shown that an increase in pulse intensity leads to transition from RSA to SA, with increased contrast, due to strong excited-state absorption. Theoretical results are in good agreement with reported experimental results. The effect of pulse intensity, pulse width, frequency and concentration has been studied to optimize the RSA to SA transition, which has been used to design all-optical picosecond NOT, AND, OR, and the universal NAND and NOR logic gates. The designs are the first application of Ru dioxolene complex based all-optical logic gates with picosecond switch off/on time. These results show the potential of transition-metal complexes for photonic applications.

Tuning the Photophysics and Reverse Saturable Absorption of Heteroleptic Cationic Iridium(III) Complexes via Substituents on the 6,6'-Bis(fluoren-2-yl)-2,2'-biquinoline Ligand.

To understand the effects of the terminal substituent at the diimine ligand on the photophysics of heteroleptic cationic Ir(III) complexes and to obtain Ir(III) complexes with extended ground-state absorption to the near-IR region while retaining the long-lived and broadly absorbing triplet excited state, we synthesized three heteroleptic cationic iridium(III) complexes bearing cyclometalating 1-phenylisoquinoline (C^N) ligands and substituted 6,6'-bis(7-R-fluoren-2-yl)-2,2'-biquinoline (N^N) ligand (R = H, NO2, or NPh2). The photophysics of these complexes was systematically investigated via spectroscopic methods and time-dependent density functional theory. All complexes possess strong ligand-localized 1π,π* transitions mixed with ligand-to-ligand charge transfer (1LLCT)/metal-to-ligand charge transfer (1MLCT) transitions below 400 nm, and a broad and featureless absorption band above 400 nm that arises from the N^N ligand-localized 1π,π*/1ILCT (intraligand charge transfer) transitions as well as the very weak 1,3LLCT/1,3MLCT transitions at longer wavelengths. The electron-withdrawing NO2 substituent on the N^N ligand leads to a blue-shift of the 1π,π*/1ILCT absorption band, while the electron-donating NPh2 substituent causes a pronounced red-shift of this band. The unsubstituted and NO2-substituted complexes (complexes 1 and 2, respectively) are moderately emissive at room temperature (RT) in solution as well as at 77 K in the glassy matrix, while the NPh2-substituted complex (3) is weakly emissive at RT, but the emission becomes much brighter at 77 K. Complexes 1 and 2 show very broad and strong triplet excited-state absorption from 460 to 800 nm with moderately long lifetimes, while complex 3 exhibits weak but broad absorption bands from 384 to 800 nm with a longer lifetime than those of 1 and 2. The nonlinear transmission experiment manifests that complexes 1 and 2 are strong reverse saturable absorbers (RSA) at 532 nm, while 3 shows weaker RSA at this wavelength. These results clearly demonstrate that it is feasible to tune the ground-state and excited-state properties of the Ir(III) complexes via the terminal substituents at the diimine ligand. By introducing the fluoren-2-yl groups to the 2,2'-biquinoline ligand to extend the diimine ligand π-conjugation, we can obtain Ir(III) complexes with reasonably long-lived and strongly absorbing triplet excited state while red-shifting their 1,3LLCT/1,3MLCT absorption band into the near-IR region. These features are critical in developing visible to near-IR broadband reverse saturable absorbers.

Tunable emission and excited state absorption induced optical limiting in Tb2(MoO4)3: Sm3+/Eu3+ nanophosphors

Photoluminescence properties and optical limiting behavior of pure and Sm3+/Eu3+ doped Tb2(MoO4)3 nanophosphors are investigated. The prepared nanophosphors exhibit excellent emission when excited by UV light. Color-tunable emissions in Tb2−xSmx(MoO4)3 and Tb2−xEux(MoO4)3 are realized by employing different excitation wavelengths or by controlling the doping concentration of Sm3+ and Eu3+. Luminescence quantum yield and CIE chromatic coordinates of the prepared phosphors were also presented. Optical limiting properties of the samples are investigated by open aperture Z-scan technique using 5 ns laser pulses at 532 nm. Numerical fitting of the measured Z-scan data to the relevant nonlinear transmission equations reveals that the nonlinear absorption is arising from strong excited state absorption, along with weak absorption saturation and it is found that the optical nonlinearity of Tb2(MoO4)3 increases with Sm3+/Eu3+doping. Parameters such as saturation fluence, excited state absorption cross section and ground state absorption cross section of the samples have been determined numerically, from which the figure of merit for nonlinear absorption is calculated. The excited state absorption cross-section of the samples is found to be one order of magnitude higher than that of the ground state absorption cross-section, indicating strong reverse saturable absorption. These results indicate that Sm3+/Eu3+ doped Tb2(MoO4)3 nanophosphors are efficient media for UV/n-UV pumped LEDs, and are also potential candidates for designing efficient optical limiting devices for the protection of human eyes and sensitive optical detectors from harmful laser radiation.

Effects of extending the π-conjugation of the acetylide ligand on the photophysics and reverse saturable absorption of Pt(ii) bipyridine bisacetylide complexes.

The synthesis and photophysics of four platinum(ii) bipyridine (bpy) bisacetylide complexes with different degrees of π-conjugation and an electron-donating diphenylamino (NPh2) or electron-withdrawing benzothiazolyl (BTZ) terminal substituent on the acetylide ligands are reported. The UV-vis absorption spectra of these complexes are composed of intense ligand-localized 1π,π* transitions at 330-430 nm and broad, moderately strong ligand-to-ligand charge transfer/metal-to-ligand charge transfer (1LLCT/1MLCT) transitions at 430-530 nm. All complexes are phosphorescent in solutions at room temperature and exhibit very broad and moderately strong triplet excited-state absorption in the visible to the NIR spectral region (425-800 nm). It is found that extending the π-conjugation of the acetylide ligands via adding one or two more ethynylfluorenyl unit(s) to the acetylide ligand does not change the energies of the 1π,π* and 1LLCT/1MLCT transitions pronouncedly except for increasing the molar extinction coefficients of the 1π,π* transitions. The emitting triplet excited states of the four complexes are the 3MLCT/3LLCT states and have the same energy. However, the complex that contains the tris(ethynylfluorenyl) units and the terminal NPh2 substituent on the acetylide ligand exhibits longer triplet lifetimes than the corresponding complex that has the bis(ethynylfluorenyl) units. The transient absorption band maxima of the complexes with tris(ethynylfluorenyl) units are slightly red-shifted in comparison to those of their respective counterparts with bis(ethynylfluorenyl) units. The nature of the terminal substituent does not influence the parentage and energies of the lowest singlet and triplet excited states. However, the triplet excited-state lifetimes of the complexes with the NPh2 terminal substituent on the bis(ethynylfluorenyl) or tris(ethynylfluorenyl) ligands are much longer than that of their counterpart with monofluorenylacetylide ligands; while the triplet lifetimes of the complexes containing the BTZ terminal substituent are similar to their counterpart with monofluorenylacetylide ligands. All complexes exhibit strong reverse saturable absorption (RSA) at 532 nm for nanosecond laser pulses.

Superior optical nonlinearity of an exceptional fluorescent stilbene dye

Strong multiphoton absorption and harmonic generation in organic fluorescent chromophores are, respectively, significant in many fields of research. However, most of fluorescent chromophores fall short of the full potential due to the absence of the combination of such different nonlinear upconversion behaviors. Here, we demonstrate that an exceptional fluorescent stilbene dye could exhibit efficient two- and three-photon absorption under the excitation of femtosecond pulses in solution phase. Benefiting from its biocompatibility and strong excited state absorption behavior, in vitro two-photon bioimaging and superior optical limiting have been exploited, respectively. Simultaneously, the chromophore could generate efficient three-photon excited fluorescence and third-harmonic generation (THG) when dispersed into PMMA film, circumventing the limitations of classical fluorescent chromophores. Such chromophore may find application in the production of coherent light sources of higher photon energy. Moreover, the combination of three-photon excited fluorescence and THG can be used in tandem to provide complementary information in biomedical studies.

Strong triplet excited-state absorption in a phenanthrolinyl iridium(III) complex with benzothiazolylfluorenyl-substituted ligands

Femtosecond transient difference absorption (fs TA) measurements, together with a series of open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies, were performed on a 1,10-phenanthrolinyl iridium(III) complex bearing ligands containing a benzothiazolylfluorenyl motif. An analysis of decay data from the fs TA experiment yields a value of 1.24±0.26 ns for the singlet excited-state lifetime τ(S) of the complex. By fitting the Z scans to a five-level dynamic model incorporating the independently measured value of τ(S) and previously reported values of the complex's triplet quantum yield (0.13) and triplet excited-state lifetime (230 ns), we obtain values of 3.5×10(-17) cm(2) (singlet) and 5.0×10(-16) cm(2) (triplet) for the excited-state absorption cross-sections of the complex in toluene solution at 532 nm; the latter value represents one of the largest triplet excited-state absorption cross-sections ever reported at this wavelength. The ratio of the triplet excited-state cross-section to the ground-state absorption cross-section exceeds 3800.

Enhanced Optical Limiting Behavior of an Indium Phthalocyanine–Single-Walled Carbon Nanotube Composite: An Investigation of the Effects of Solvents

The nonlinear optical behavior of 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (2) and its carbon nanotube composite in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) solutions is described. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. A large nonlinear absorption that increased on covalent linking with single-walled carbon nanotubes (SWCNTs) was observed for the compound in DMSO. The nanosecond nonlinear absorption and the optical limiting behavior of this complex are shown to be dominated by a strong excited state absorption from a two-photon pumped state. The optical limiter using the new nanocomposite material (SWCNT-2) in the appropriate solvent showed a much lower threshold for optical limiting together with a much lower transmission at high fluences than previously reported nanocomposite limiters. The optical properties of the phthalocyanine and its conjugate were found to show high sensitivity toward the change of solvent matrix.

Spectroscopic characterization and pulsed laser operation of Eu3+:KGd(WO4)2 crystal

Europium-doped monoclinic potassium gadolinium tungstate KGd(WO4)2 crystals are grown by the top-seeded solution growth (TSSG) technique. Their absorption spectra are studied in detail for principal light polarizations, E ∥ Np, Nm and Ng. It is accompanied by determination of absorption oscillator strengths by means of the theory of f–f transition intensities for systems with anomalously strong configuration interaction. Spectral and temporal characteristics of luminescence associated with 5D0 → 7FJ transitions are analyzed, and luminescence branching ratios and the radiative lifetime of the 5D0 state are determined. Stimulated-emission cross-section spectra are evaluated for Eu:KGd(WO4)2 crystal. Pulsed Eu:KGd(WO4)2 lasers operating at room temperature at the wavelength of 702.8 nm (5D0 → 7F4 transition) are studied at Eu concentration of 10/25 at.%. Under laser pumping at 533.6 nm, a maximum output energy of 570 μJ is obtained. The main limitation for laser operation at 5D0 → 7F2 transition is strong excited-state absorption via the 5D0 → 5F4 channel.

Platinum Chloride Complexes Containing 6-[9,9-Di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2′-bipyridine Ligand (R = NO2, CHO, Benzothiazol-2-yl, n-Bu, Carbazol-9-yl, NPh2): Tunable Photophysics and Reverse Saturable Absorption

Six new platinum(II) chloride complexes 1-6 containing a 6-[9,9-di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2'-bipyridine (R = NO2, CHO, benzothiazol-2-yl (BTZ), n-Bu, carbazol-9-yl (CBZ), NPh2) ligand were synthesized and characterized. The influence of the electron-donating or electron-withdrawing substituent at the 7-position of the fluorenyl component on the photophysics of these complexes was systematically investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). Electron-withdrawing or -donating substituents exert distinct effects on the photophysics of the complexes. All complexes feature a low-energy, broad (1)MLCT (metal-to-ligand charge transfer)/(1)ILCT (intraligand charge transfer)/(1)π,π* absorption band (tail) above ca. 430 nm and a major absorption band(s) between 320 and 430 nm, which admix (1)MLCT, (1)π,π*, (1)ILCT, and/or (1)LLCT (ligand-to-ligand charge transfer) characters. The contributions of different configurations to the major absorption band(s) vary depending on the nature of the substituent. Strong electron-donating or -withdrawing substituents (NPh2 and NO2) and the aromatic substituent BTZ cause a pronounced red-shift of the absorption spectra of 1, 3, and 6. All complexes are emissive at room temperature and at 77 K. The emitting excited state is dominated by (3)π,π* character in 1-3, with some contributions from (3)MLCT in 1 and 2, while the emission is predominantly from the (3)MLCT state for 4 and 5 but with some (3)π,π* character. For 6, the emitting state is (3)ILCT in nature. With the increased electron-donating ability of the substituent, the (3)π,π* character diminishes while charge transfer character increases. All complexes exhibit broad and strong triplet excited-state absorption (TA) from the near-UV to the near-IR spectral region. The TA band maxima are red-shifted for complexes 1-3 (which possess the electron-withdrawing substituents) compared to those of 4-6 (which contain electron-donating substituents). All complexes manifest strong reverse saturable absorption (RSA) for a nanosecond laser pulse at 532 nm, which originates from the much stronger triplet excited-state absorption than the ground-state absorption of 1-6 in the visible spectral region. The strength of RSA follows this trend: 4 ≈ 5 < 1 ≈ 3 < 2 < 6, which is primarily determined by the ratio of the triplet excited-state absorption cross section relative to that of the ground-state absorption (σex/σ0) at 532 nm. The σex/σ0 ratios (116-261) of 1-6 at 532 nm are much larger than those of most of the reverse saturable absorbers reported in the literature, with the ratio of 6 (σex/σ0 = 261) being among the largest values reported to date. This makes complexes 1-6, especially 6, very promising reverse saturable absorbers.

Er3+ ions doped bismuthate glasses sensitized by Yb3+ ions for highly efficient 2.7 μm laser applications

In present study, we investigated the emissions from visible to mid-infrared and energy transfer processes in Er3+/Yb3+ co-doped germanate–gallate–bismuthate (BGG) glasses. Larger absorption cross-section of Yb3+ ions (7.5×10−21cm2) and enhanced up-conversion, near-infrared and mid-infrared emissions indicate that the introduced sensitized Yb3+ ions can efficiently absorb and transfer pumping energy (980nm) to activate the Er3+ ions. The intensity of 2.7μm emission in Er3+/Yb3+ co-doped samples is about 3 times higher than that of Er3+ singly doped sample. But, the intensity of 2.7μm emission decreases with excessive Yb3+ ions. The optimized ratio of Er3+ and Yb3+ ions for 2.7μm emission is 1.0:0.2 in this BGG glasses. Large emission cross-section σe (−13×10−21cm2 and −9.57×10−21cm2 for 2.7μm and 1.5μm emissions, respectively) is obtained in Er3+/Yb3+ co-doped BGG glasses. According to absorption and emission spectra, energy transfer processes between Yb3+ and Er3+ ions were proposed and main reason for increased up-conversion is the strong excited state absorption (ESA) from excited Er3+ ions at 4I11/2 and 4I13/2 levels. Therefore, high pumping efficiency, intense emissions, large emission cross-section of 2.7μm and 1.5μm emissions and efficient energy transfer processes in this Er3+/Yb3+ co-doped BGG glasses hints its potential applications in laser materials, especially in 2.7μm wavelength.

Ultrafast ring-opening reactions: a comparison of α-terpinene, α-phellandrene, and 7-dehydrocholesterol with 1,3-cyclohexadiene

The excited and ground state dynamics of a series of 1,3-cyclohexadiene derivatives and their hexatriene photoproducts are studied using ultrafast broadband UV-visible transient absorption spectroscopy. The substitution pattern around the cyclohexadiene backbone alters the excited state potential energy surface in the Franck-Condon region as evidenced by changes in the excited state absorption and fluorescence properties of the systems. Unsubstituted 1,3-cyclohexadiene and alpha-phellandrene exhibit no excited state absorption while a strong excited state absorption in the visible spectral region is observed for both alpha-terpinene and Provitamin D3. Steric factors introduced by the ring substitutions determine the dominant rotational isomer at equilibrium for the hexatriene photoproducts. Coupling to the solvent during the conformational relaxation from the initial helical all-cis hexatriene is unique to each photoproduct, but the relaxation process occurs on a 6-10 ps timescale regardless of the size or substitution pattern on the triene.

Impact of the Synergistic Collaboration of Oligothiophene Bridges and Ruthenium Complexes on the Optical Properties of Dumbbell-Shaped Compounds

The linear and non-linear optical properties of a family of dumbbell-shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2'-bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non-linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4, with 3 and 6 thiophene rings, respectively), owing to the presence of the (3)π-π* state of the conjugated bridge below the (3)MLCT-emitting states of the end-capping Ru(II) complexes. In contrast, the compound with the shortest bridge (2, one thiophene ring) shows excellent photophysical features. Non-linear optical experiments showed that the investigated compounds were strong non-linear absorbers in wide energy ranges. Indeed, their non-linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two-photon absorption (TPA) but also noteworthy three-photon-absorption behavior, with a cross-section value of 4×10(-78) cm(6) s(2) at 1450 nm. This characteristic was complemented by the strong excited-state absorption (ESA) that was observed for compounds 3 and 4. As a matter of fact, the overlap between the non-linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical-power-limiting applications.

The synthesis and NLO properties of 1,8-naphthalimide derivatives for both femtosecond and nanosecond laser pulses

Four 1,8-naphthalimide derivatives were synthesized for new nonlinear optical(NLO) materials. Hydrazone group as a p-π structure was introduced into the molecule to extend conjugation and produce NLO properties. Their linear and nonlinear optical (NLO) properties were studied in details. The results show that these compounds possess strong excited-state absorption (ESA) properties and optical limiting with nanosecond laser pulses at 532 nm. Moreover, they also preserve the luminescence originated from naphthalimide and two-photon absorption (TPA) behaviour which can be observed under femtosecond laser pulses ranged from 750 to 870 nm. The broad-band optcial limiting properties of these compounds indicate that they can be potentially applicated in optical limiting materials.

Two-Photon Mediated Three-Photon Fluorescence: Lessons from a Quinoidal Oligothiophene Dimer

Detailed here is the use of NIR femtosecond pulsed excitation to drive three-photon absorption (3PA) in a cyano-terminated quinoidal oligothiophene (QOT) dimer to the exclusion of all other fluorescing processes, resulting in 3PA emission bright enough to be visible by eye. Through steady-state, multiphoton, and ultrafast transient spectroscopy, it is shown that despite competing nonlinear optical processes, such as an available two-photon transition (2PA) and excited-state absorption (ESA), emission characteristics remain an I3 process explicitly due to 3PA. Specifically, we will show the viability of a two-photon transition at the pump wavelength and strong ESA; neither occurs to a significant degree in this QOT system when pump energies match both a virtual state near resonant with a viable 2PA state and a higher-lying 3PA energy level. This study provides a clear method for evaluating multiband 3PA emitters, which bypasses much of the ambiguity observed in purely absorption based studies where 2PA, ESA, and 3PA may all contribute to signal and are difficult to distinguish. Additionally, this study introduces a rigid, molecular wire-like thiophene oligomer as a strong nonlinear optical responsive material with gross response changes based on small changes in IR excitation.

Excited state absorption measurement in the 900-1250 nm wavelength range for bismuth-doped silicate fibers

The feasibility of direct laser diode pumping of Bi-doped fiber lasers at the wavelengths of 915 and 975 nm was examined by measuring excited state absorption in Bi-doped silicate fibers for the wavelength range of 900-1250 nm. When the Bi-doped fibers were pumped at 1047 nm a strong excited state absorption was found at 915 and 975 nm, whereas no significant excited state absorption was observed in the 1080 nm pumping band nor in the emission band, approximately 1160 nm, of Bi-doped fiber lasers.

Photophysical and spectroscopic manifestations of the low-lying πσ* state of 4-(dimethylamino)benzethyne: solvent-polarity dependence of fluorescence and excited-state absorptions

A concerted experimental and computational study of 4-(dimethylamino)benzethyne, DMABE, has been carried out to probe the low-lying pisigma* state and the role it plays in the photophysics of the molecule. The subpicosecond transient absorption spectra reveal the presence of a strong excited-state absorption at about 700 nm and a weaker absorption at about 520 nm. The observed absorption maxima are in excellent agreement with the TDDFT calculations that place a strongly allowed pisigma* <--pisigma* transition at 750 nm, and a weaker pipi* <--pipi* (LE) transition at 528 nm. This agreement combined with the differing decay times, and differing solvent shifts of the two transients, allow assignments of the 700 nm absorption to the pisigma* state and the 520 nm absorption to the LE (pipi*) state. The bifurcation of the initially excited L(a) (pipi*) state into the pisigma* state and the LE state, as probed by transient absorption, is strongly influenced by solvent polarity, with polar environments favoring the L(a)-->pisigma* decay channel over the competing L(a)--> LE decay channel. The nanosecond radiationless decay of the LE state to the dark pisigma* state is also strongly enhanced in polar environments, thus accounting for the dramatic quenching of fluorescence in solvents of high polarity.

Third-Order Optical Nonlinearity in Novel Porphyrin Dimers

We investigate the third-order optical nonlinearities in four novel porphyrin dimers (dimers A to D) and a monomeric porphyrin H2CPTPP measured by using the single-beam z-scan technique with a pulsed Q-switched Nd:YAG nanosecond laser at 532nm. All the samples show strong excited state absorption (ESA) and high value of χ(3) in the ns domain at this wavelength. We perform a comparison between dimer A and its monomer H2CPTPP in their third-order optical nonlinearity, and discuss the relationships between the values of χ(3) and the different bridging groups for all the dimers.

∼2 μm Tm3+/Yb3+-doped tellurite fibre laser

We present, for the first time, laser emission in the range 1.910–1.994 μm in Tm3+/Yb3+-doped tellurite fibre when pumped using an Yb3+-doped double-clad silica fibre laser operating at 1.088 μm. With this pump scheme there was strong pump excited state absorption (ESA) which caused upconversion emission at 800 nm and 480 nm due to the Tm3+: 3H4 → 3H6 and Tm3+: 1G4 → 3H6 transitions, respectively. This strong ESA limited the maximum slope efficiency to 10% with respect to absorbed pump power, and the maximum output power to 67 mW. This is however the highest output power which has been achieved in a tellurite fibre laser so far. The lowest observed threshold was 114 mW for a 22 cm long fibre and a 90% reflective output coupler. Further power scaling was limited due to thermal damage at the pump end of the fibre. The optimum fibre length for this arrangement was around 16 cm but lasing was achieved in lengths ranging from <9 to 30 cm. Tellurite glass offers significant advantages over silicate and fluoride glasses which make it a very promising material for compact, medium power, near and mid-IR fibre lasers for range-finding, medical and atmospheric monitoring and sensing applications.

Axial Halogen Ligand Effect on Photophysics and Optical Power Limiting of Some Indium Naphthalocyanines

Three axially substituted complexes, 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium chloride (1a), 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium bromide (1b), and 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium iodide (1c) have been synthesized and their photophysical properties have been investigated. Optical power limiting of nanosecond (ns) and picosecond (ps) laser pulses at 532 nm using these complexes has been demonstrated. All complexes display strong Q(0,0) absorption and measurable emission in the near-infrared region and exhibit strong excited-state absorption in the range of 470-700 nm upon ns laser excitation. The different axial ligands show negligible effect on the linear absorption, emission, and transient difference absorption spectra. However, the excited-state lifetime, triplet excited-state quantum yield, and efficiency to generate singlet oxygen are affected significantly by the heavier axial ligand. Brominated and iodinated complexes 1b and 1c show higher triplet excited-state quantum yield, while chlorinated complex 1a has longer excited-state lifetime and is more efficient in generating singlet oxygen. The iodinated complex 1c displayed the best optical limiting due to the higher ratio of excited-state absorption cross section to ground state absorption cross section (sigma(eff)/sigma(0)).