Ahmet Karatay

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.

DiiodoBodipy-Perylenebisimide Dyad/Triad: Preparation and Study of the Intramolecular and Intermolecular Electron/Energy Transfer

2,6-diiodoBodipy-perylenebisimide (PBI) dyad and triad were prepared, with the iodoBodipy moiety as the singlet/triplet energy donor and the PBI moiety as the singlet/triplet energy acceptor. IodoBodipy undergoes intersystem crossing (ISC), but PBI is devoid of ISC, and a competition of intramolecular resonance energy transfer (RET) with ISC of the diiodoBodipy moiety is established. The photophysical properties of the compounds were studied with steady-state and femtosecond/nanosecond transient absorption and emission spectroscopy. RET and photoinduced electron transfer (PET) were confirmed. The production of the triplet state is high for the iodinated dyad and the triad (singlet oxygen quantum yield ΦΔ = 80%). The Gibbs free energy changes of the electron transfer (ΔGCS) and the energy level of the charge transfer state (CTS) were analyzed. With nanosecond transient absorption spectroscopy, we confirmed that the triplet state is localized on the PBI moiety in the iodinated dyad and the triad. An exceptionally long lived triplet excited state was observed (τT = 150 μs) for PBI. With the uniodinated reference dyad and triad, we demonstrated that the triplet state localized on the PBI moiety in the iodinated dyad and triad is not produced by charge recombination. These information are useful for the design and study of the fundamental photochemistry of multichromophore organic triplet photosensitizers.

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).

Near-IR Broadband-Absorbing trans-Bisphosphine Pt(II) Bisacetylide Complexes: Preparation and Study of the Photophysics

Broadband near-IR absorbing trans-bis(trialkylphosphine) Pt(II) bisacetylide binuclear complex (Pt-1) was prepared with boron-dipyrromethene (Bodipy) and styrylBodipy acetylide ligands. Pt-1 shows strong absorption bands at 731 and 503 nm. Singlet energy transfer (EnT) and efficient intersystem crossing of the central coordinated Bodipy ligand were proposed to be responsible for the efficient funneling of the excitation energy to the triplet-state manifold. Reference complexes containing only a single Bodipy ligand were prepared for comparison (with styrylBodipy ligand Pt-0 or Bodipy ligand Pt-2). The molecular structures were confirmed by single-crystal X-ray diffraction. The photophysical properties were studied with steady-state and time-resolved transient absorption spectroscopies, electrochemical characterization, and density functional theory/time-dependent density functional theory calculations. Dual fluorescence was observed for Pt-1. Singlet EnT in Pt-1 was proposed based on the fluorescence quenching/excitation spectra, and femtosecond transient absorption spectra (energy transfer rate constant kEnT = 2.2 × 10(10) s(-1)). With nanosecond transient absorption spectra, intramolecular triplet-state energy transfer in Pt-1 was proved. Gibbs free energy changes of charge separation indicate that the photoinduced intramolecular electron transfer in Pt-1 is thermodynamically prohibited. Intermolecular triplet transfer between Pt-2 and L-1 was studied with nanosecond transient absorption spectra; the EnT rate and energy transfer efficiency were determined as 3.6 × 10(4) s(-1) and 94.5%, respectively. The singlet oxygen ((1)O2) photosensitizing of Pt-1 was improved as compared to the complexes containing only a single visible-light-absorbing chromophore.

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.

trans-Bis(alkylphosphine) platinum(II)-alkynyl complexes showing broadband visible light absorption and long-lived triplet excited states

Heteroleptic trans-bis(alkylphosphine) platinum(II) bisacetylide complexes Pt-1 and Pt-2 were prepared to achieve broadband absorption of visible light. Two different ethynylBodipy ligands, 2-ethynylBodipy and 2,6-diethynylBodipy or 8-(4′-ethynylphenyl)Bodipy, were used in each complex. Each Bodipy ligand gives strong absorption in the visible spectral region, but at different wavelengths, thus broadband absorption in the visible spectral region was achieved for the Pt(II) complexes (e is up to 1.85 × 105 M−1 cm−1 in the region of 450–700 nm). Singlet energy transfer from the peripheral coordinated Bodipy to the central coordinated Bodipy (with 2,6-diethynyl substitution) was confirmed by steady state absorption/luminescence spectroscopy, fluorescence excitation spectroscopy and nanosecond/femtosecond ultrafast time-resolved transient absorption spectroscopy. Long-lived triplet excited states were observed for both complexes (τT = 63.13 μs for Pt-1 and τT = 94.18 μs for Pt-2). Nanosecond time-resolved transient absorption spectroscopy indicated that the triplet excited state of Pt-1 is distributed on both Bodipy units. For Pt-2, however, the T1 state is confined to the central coordinated Bodipy ligand. These complexes show high singlet oxygen (1O2) quantum yields (ΦΔ = 76.0%). With nanosecond pulsed laser excitation, delayed fluorescence was observed for the complexes (τDF = 43.8 μs for Pt-1 and τDF = 111.0 μs for Pt-2), which is rarely reported for transition metal complexes. The complexes were used as efficient multi-wavelength excitable triplet photosensitizers for triplet–triplet annihilation upconversion.

Radical-Enhanced Intersystem Crossing in New Bodipy Derivatives and Application for Efficient Triplet–Triplet Annihilation Upconversion

A long-lived triplet excited state of the well-known fluorophore boron dipyrromethene (Bodipy) was observed for the first time via efficient radical-enhanced intersystem crossing (EISC). The triplet state has been obtained in two dyads in which the Bodipy unit is linked to a nitroxide radical, 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), with two different length spacers. The photophysical properties were studied with steady-state and time-resolved transient optical spectroscopies and electron spin resonance (cw-ESR and TR-ESR). The fluorescence of Bodipy units is significantly quenched in the dyads, and the spin-polarized TEMPO signals were observed with TR-ESR, generated by a radical triplet pair mechanism. Efficient EISC (ΦT = 80%) was observed for the dyad with a shorter linker, and the triplet state lifetime of the Bodipy chromophore is exceptionally long (62 μs). The EISC takes 250 ps. Poor ISC was observed for the dyad with a longer linker. The efficient ISC and long-lived triplet excited state in this flexible system are in stark contrast to the previously studied rigid EISC systems. The EISC effect was employed for the first time to perform triplet-triplet annihilation (TTA) upconversion (quantum yield ΦUC = 6.7%).

Fabrication of Supramolecular n/p-Nanowires via Coassembly of Oppositely Charged Peptide-Chromophore Systems in Aqueous Media

Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor-acceptor (D-A) domains. We synthesized n-type and p-type β-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble via hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D-A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A-D-A unit cells having an association constant (KA) of 5.18 × 105 M-1. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics.

Fabrication of Plasmonically Active Substrates using Engineered Silver Nanostructures for SERS Applications

Demanding applications in sensing, metasurfaces, catalysis, and biotechnology require fabrication of plasmonically active substrates. Herein, we demonstrate a bottom-up, versatile, and scalable approach that relies on direct growth of silver nanostructures from seed particles that were immobilized on polymer brush-grafted substrates. Our approach is based on (i) the uniform and tunable assembly of citrate-stabilized gold nanoparticles on poly(ethylene glycol) brushes to serve as seeds and (ii) the use of hydroquinone as a reducing agent, which is extremely selective to the presence of seed particles, confining the growth of silver nanostructures on the surface of the substrate. The diameter of the seed particles, concentration, as well as ratio of reactants and duration of the growth process are investigated for large-area growth of silver nanostructures with high surface coverage and plasmonic activity. The resulting silver nanostructures exhibit high levels of surface-enhanced Raman scattering activity at two different laser lines and allow detection of molecules at concentrations as low as 10 pM. The plasmonic properties of the silver nanostructures are further studied using ultrafast pump-probe spectroscopy. Spatially defined silver nanostructures are fabricated through the seed particles that are patterned via soft lithography, showing the capabilities of the presented approach in device applications.