H. Gul Yaglioglu

BODIPY triads triplet photosensitizers enhanced with intramolecular resonance energy transfer (RET): broadband visible light absorption and application in photooxidation

Resonance energy transfer (RET) was used to enhance the light absorption in triad triplet photosensitizers to access strong and broadband absorption in visible region (from 450–750 nm). This strategy was demonstrated by preparation of (BODIPY)2-diiodo-aza-BODIPY triad (B-2) and (carbazole-styryl BODIPY)2-diiodo-aza-BODIPY triad (B-3), in which the energy donor (BODIPY or styryl-BODIPY) and the energy acceptor (aza-BODIPY, also as the spin converter) parts were connected by click chemistry. Both the energy donors and the energy acceptors show strong absorption in the visible spectral region, but at different wavelengths, therefore the triads show broadband absorption in visible spectra region, e.g. the two major absorption bands of B-3 are located at 593 nm and 683 nm, with e up to 220000 M−1 cm−1 and 81000 M−1 cm−1, respectively. For comparison, a reference compound with only diiodo-aza-BODIPY as the light-harvesting unit was prepared (B-1), which shows only one major absorption band in visible spectral region. Fluorescence studies indicated intramolecular energy transfer for these BODIPY hybrids, a conclusion which is supported by the femtosecond time-resolved transient absorption spectroscopy. Nanosecond transient absorption spectra show that triplet excited states of the dyad and the triad are localized on the iodo-aza-BODIPY part. The compounds were used as triplet photosensitizers for singlet oxygen (1O2) mediated photooxidation of 1,5-dihydroxylnaphthalene and the photosensitizing ability of the new triplet photosensitizers are more efficient than the mono-chromophore based triplet photosensitizers. The molecular design rationale of these RET-enhanced multi-chromophore triplet photosensitizer is useful for development of efficient triplet photosensitizers and for their applications in photocatalysis, photodynamic therapy, photovoltaics and upconversion.

Good optical limiting performance of indium and gallium phthalocyanines in a solution and co-polymer host

The optical limiting characteristics of tetra- and octasubstituted gallium and indium phthalocyanine complexes have been studied by means of the open-aperture Z-scan technique with nanosecond pulses at 532 nm. The nonlinear response demonstrated that all investigated compounds exhibited strong reverse saturable absorption for both solution and solid-state-based experiments. The results showed that the ratio of the excited to ground state absorption cross section κ and effective nonlinear absorption coefficient βeff are largely dependent on the linear absorption coefficient. All compounds in chloroform exhibited almost the same optical limiting performance at the same linear absorption coefficient. Pc/PMMA composite films display a much larger effective nonlinear absorption coefficient, lower ratio of the excited to ground state absorption cross section and lower saturation fluence for optical limiting when compared to the same Pc molecules in solution. All gallium and indium complexes of phthalocyanines are good candidates for optical limiting applications.

Synthesis, characterization and nonlinear absorption of novel octakis-POSS substituted metallophthalocyanines and strong optical limiting property of CuPc

In this study, the preparation of some novel metallophthalocyanine (MPcs) complexes substituted with octakis(mercaptopropylisobutyl-POSS) functional group was achieved. By the reaction of [1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane 1 with 4,5-dichloro-1,2-dicyanobenzene 2 in THF as the solvent in the presence of K2CO3 as the base, the phthalonitrile derivative 3 was synthesized. Compound 3 reacted with CoCl2 x 6H2O in ethylene glycol to furnish a novel cobalt(II) phthalocyanine . The tetramerization of 3 with urea and CuCl in the absence of solvent gave the novel Cu(II) phthalocyanine 4; while with Zn(OAc)2 x 2H2O in dry DMF gave the novel zinc(ii) phthalocyanine 6. The structures of the target compounds were confirmed by elemental analysis, UV/VIS, IR, MALDI-TOF MS and 1H NMR spectra. Nonlinear absorptions of MPcs in chloroform solution were investigated by using Z-scan measurement technique with 4 ns pulses at 532 nm wavelength. While CuPc 5 showed very high nonlinear absorption, MPcs 4 and 6 did not show considerable nonlinear absorption. Investigations of optical limiting properties of 5 revealed that this material is a very good candidate for optical limiting applications.

Nonlinear and saturable absorption characteristics of amorphous InSe thin films

We prepared very thin amorphous InSe films and investigated the thickness dependence of the nonlinear absorption by pump-probe and open aperture Z-scan techniques. While thinner films (20 and 52 nm) exhibit saturable absorption, thicker films (70 and 104 nm) exhibit nonlinear absorption for 4 ns, 65 ps, and 44 fs pulse durations. This behavior is attributed to increasing localized defect states in the energy band gap as the film thickness increases. We developed a theoretical model incorporating one photon, two photon, and free carrier absorptions and their saturations to derive the transmission in the open aperture Z-scan experiment. The theory of open aperture Gaussian beam Z-scan based on the Adomian decomposition method was used to fit the experimental curves. Nonlinear absorption coefficients along with saturation intensity thresholds were extracted from fitting the experimental results for all pulse durations. The lowest saturation threshold was found about 3×10−3 GW/cm2 for 20 nm film thickness wit...

Electrochemically tunable ultrafast optical response of graphene oxide

dation. Here, we study the effect of the oxidation level on nonlinear optical properties of GO. We demonstrate that both electrochemically induced reversible reduction and optically induced photoreduction in GO result in changes in the nonlinear optical properties of GO thin films. We present the carrier dynamics and nonlinear optical properties of such films, studied by ultrafast wavelength-dependent pumpprobe spectroscopy. We show that ultrafast response of GO can be tuned by both reduction procedure. The preparation, characterization, linear optical, and electrochromism properties of GO were very recently reported. 10 We study the electrical reduction in GO in air, using multilayer GO thin films deposited on metalized glass substrates. The two terminal devices consist of thin 10‐50 nm Pd/Au planar contacts, separated by 0.3‐0.6 mm, with a thin multilayer GO film covering both contacts and in between Fig. 1a. The degree of chemical reduction and linear absorption spectrum can be tuned by applying a

Resonance energy transfer-enhanced rhodamine–styryl Bodipy dyad triplet photosensitizers

Organic triplet photosensitizers (R-1 and R-2) enhanced with the resonance energy transfer (RET) effect were prepared. Rhodamine was used as an intramolecular energy donor, and iodo-styryl-Bodipy was used as intramolecular energy acceptor/spin converter. Both the energy donor and energy acceptor in R-1 and R-2 give strong absorption in the visible region but at different wavelengths (e.g. for R-1, e = 120 000 M−1 cm−1 at 557 nm for the energy donor and e = 73 300 M−1 cm−1 at 639 nm for the energy acceptor). As a result, the photosensitizers show broadband absorption in the visible spectral region. In comparison, conventional triplet photosensitizers contain only one visible light-harvesting chromophore; thus, there is usually only one major absorption band in the visible spectral region. Using steady state and time-resolved spectroscopy, we demonstrated that photoexcitation in the energy donor was followed by intramolecular singlet energy transfer, and then via intersystem crossing (ISC) of the energy acceptor (spin converter), triplet excited states localized on the iodo-styryl-Bodipy were produced, which was confirmed by nanosecond time-resolved transient difference absorption spectroscopy. The organic dyad triplet photosensitizers were used for photoredox catalytic organic reactions to prepare pyrrolo[2,1-a]isoquinoline, and we found that the photocatalytic capability was improved with the RET effect. The dyads were also used as fluorescent stains for LLC cancer cells. Photodynamic effect was observed with the same cells, which were killed on photoirradiation with 635 nm red-emitting LED after incubation with the triplet photosensitizers. Therefore, these photosensitizers can be potentially developed as dual functional theranostic reagents. Using the molecular structural protocol reported herein, organic triplet photosensitizers with strong broadband absorption in the visible spectral region and predictable ISC can be easily designed. These results are useful for the study of organic triplet photosensitizers in the area of organic photochemistry/photophysics, photoredox catalytic organic reactions and photodynamic therapy (PDT).

Probing ultrafast energy transfer between excitons and plasmons in the ultrastrong coupling regime

We investigate ultrafast energy transfer between excitons and plasmons in ensembles of core-shell type nanoparticles consisting of metal core covered with a concentric thin J-aggregate (JA) shell. The high electric field localization by the Ag nanoprisms and the high oscillator strength of the JAs allow us to probe this interaction in the ultrastrong plasmon-exciton coupling regime. Linear and nonlinear optical properties of the coupled system have been measured using transient absorption spectroscopy revealing that the hybrid system shows half-plasmonic and half-excitonic properties. The tunability of the nanoprism plasmon resonance provides a flexible platform to study the dynamics of the hybrid state in a broad range of wavelengths.

The effect of thickness and/or doping on the nonlinear and saturable absorption behaviors in amorphous GaSe thin films

We investigated the nonlinear and saturable absorption characteristics of very thin amorphous undoped GaSe, Ge (0.01 at. %), and Sn (0.5 at. %) doped GaSe films by pump-probe and open aperture Z-scan techniques. Linear absorption measurements indicate blueshift in energy with increasing film thickness. Thinner films exhibit saturable absorption while thicker films exhibit nonlinear absorption for 4 ns and 65 ps pulse durations. The films exhibit competing effects between nonlinear and saturable absorption. Saturable absorption behavior weakens while nonlinear absorption appears with increasing film thickness. In addition to that, saturable absorption behavior is very sensitive to doping. Doping causes absorption behaviors to appear in thinner films compared to undoped films. These behaviors are attributed to increasing localized defect states with increasing film thickness and doping. To derive the transmission in open aperture Z-scan data, a theoretical model incorporating one photon, two photon, and fre...

Encapsulation of a zinc phthalocyanine derivative in self-assembled peptide nanofibers

In this article, we demonstrate encapsulation of octakis(hexylthio) zinc phthalocyanine molecules by non-covalent supramolecular organization within self-assembled peptide nanofibers. Peptide nanofibers containing octakis(hexylthio) zinc phthalocyanine molecules were obtained via a straight-forward one-step self-assembly process under aqueous conditions. Nanofiber formation results in the encapsulation and organization of the phthalocyanine molecules, promoting ultrafast intermolecular energy transfer. The morphological, mechanical, spectroscopic and non-linear optical properties of phthalocyanine containing peptide nanofibers were characterized by TEM, SEM, oscillatory rheology, UV-Vis, fluorescence, ultrafast pump–probe and circular dichroism spectroscopy techniques. The ultrafast pump–probe experiments of octakis(hexylthio) zinc phthalocyanine molecules indicated pH controlled non-linear optical characteristics of the encapsulated molecules within self-assembled peptide nanofibers. This method can provide a versatile approach for bottom-up fabrication of supramolecular organic electronic devices.

Femtosecond laser crystallization of amorphous Ge

Ultrafast crystallization of amorphous germanium (a-Ge) in ambient has been studied. Plasma enhanced chemical vapor deposition grown a-Ge was irradiated with single femtosecond laser pulses of various durations with a range of fluences from below melting to above ablation threshold. Extensive use of Raman scattering has been employed to determine post solidification features aided by scanning electron microscopy and atomic force microscopy measurements. Linewidth of the Ge optic phonon at 300 cm−1 as a function of laser fluence provides a signature for the crystallization of a-Ge. Various crystallization regimes including nanostructures in the form of nanospheres have been identified.