Triplet Sensitization Research Articles

ChemInform Abstract: A Novel Photodimerization of 4‐Aryl‐4H‐pyrans for Cage Compounds.

AbstractThe [2 + 2] dimerization of pyrans (I) in the presence of benzophenone as triplet sensitizer gives C2‐symmetric 3,9‐dioxatetraasteranes in low yields.

Monitoring oxygen concentration during photodynamic therapy using prompt photosensitizer fluorescence

A novel technique is described that uses either time-resolved or steady state prompt photosensitizer fluorescence to measure local oxygen concentration. Solution experiments conducted with Al(III) phthalocyanine chloride tetrasulfonic acid confirmed that the steady state fluorescence signal is dependent on the oxygen concentration and fluence rate. A relationship between prompt sensitizer fluorescence and sensitizer triplet quenching efficiency is derived which does not require knowledge of the Stern–Volmer constant. Similar relationships are also derived for sensitizer delayed fluorescence and phosphorescence. An explicit photodynamic therapy (PDT) dose metric that incorporates light dosimetry, sensitizer dosimetry, and triplet quenching efficiency is introduced. All components of this metric can be determined by optical measurements.

New Anthracene Derivatives as Triplet Acceptors for Efficient Green‐to‐Blue Low‐Power Upconversion

Three new anthracene derivatives [2-chloro-9,10-dip-tolylanthracene (DTACl), 9,10-dip-tolylanthracene-2-carbonitrile (DTACN), and 9,10-di(naphthalen-1-yl)anthracene-2-carbonitrile (DNACN)] were synthesized as triplet acceptors for low-power upconversion. Their linear absorption, single-photon-excited fluorescence, and upconversion fluorescence properties were studied. The acceptors exhibit high fluorescence yields in DMF. Selective excitation of the sensitizer Pd(II)octaethylporphyrin (PdOEP) in solution containing DTACl, DTACN, or DNA-CN at 532 nm with an ultralow excitation power density of 0.5 W cm(-2) results in anti-Stokes blue emission. The maximum upconversion quantum yield (Φ(UC) =17.4%) was obtained for the couple PdOEP/DTACl. In addition, the efficiency of the triplet-triplet energy transfer process was quantitatively studied by quenching experiments. Experimental results revealed that a highly effective acceptor for upconversion should combine high fluorescence quantum yields with efficient quenching of the sensitizer triplet.

Triplet Sensitization in an Anionic Poly(phenyleneethynylene) Conjugated Polyelectrolyte by Cationic Iridium Complexes

We describe a systematic study of triplet sensitization in a poly(phenyleneethynylene) conjugated polyelectrolyte (CPE) in methanol solution by using a series of three cationic iridium complexes with varying triplet energy. The cationic iridium complexes bind to the anionic CPE by ion-pairing, leading to singlet state quenching of the polymer, and allowing for efficient back-transfer of triplet excitation energy to the polymer. Efficient (amplified quenching) of the polymer's fluorescence is observed for each iridium complex, with Stern-Volmer quenching constants in excess of 10(5) M(-1). Triplet sensitization is confirmed for two of the iridium complexes by monitoring the relative yield of the CPE triplet state by transient absorption spectroscopy. One of the iridium complexes does not sensitize the CPE triplet, and consideration of the energies of the three complexes allows us to bracket the triplet energy of the CPE within the range 1.95-2.26 eV.

Providing power for miniaturized medical implants: triplet sensitization of semiconductor surfaces

Here, we recognize the growing significance of miniaturized devices as medical diagnostic tools and highlight the need to provide a convenient means of powering such instruments when implanted into the body. One of the most promising approaches to this end involves using a light-collection facility to absorb incident white light and transfer the photonic energy to a tiny semiconductor embedded on the device. Although fluorescent organic molecules offer strong potential as modules for such solar collectors, we emphasize the promise offered by transition metal complexes. Thus, an extended series of binuclear Ru(II)/Os(II) poly(pyridine) complexes has been shown to be highly promising sensitizers for amorphous silicon solar cells. These materials absorb a high fraction of visible light while the Ru(II)-based units possess triplet energies that are comparable to those of the naphthalene-based bridge. The metal complex injects a triplet exciton into the bridge and this, in turn, is trapped by the Os(II)-based terminal. The result is extremely efficacious triplet-energy transfer; at room temperature the rate of energy transfer is independent of distance over some 6 nm and only weakly dependent on temperature.

Time-Resolved EPR Study of Singlet Oxygen in the Gas Phase

X-band EPR spectra of singlet O2((1)Δg) and triplet O2((3)Σg(-)) were observed in the gas phase under low molecular-oxygen pressures PO2 = 0.175-0.625 Torr, T = 293-323 K. O2((1)Δg) was produced by quenching of photogenerated triplet sensitizers naphthalene C8H10, perdeuterated naphthalene, and perfluoronaphthalene in the gas phase. The EPR spectrum of O2((1)Δg) was also observed under microwave discharge. Integrated intensities and line widths of individual components of the EPR spectrum of O2((3)Σg(-)) were used as internal standards for estimating the concentration of O2 species and PO2 in the EPR cavity. Time-resolved (TR) EPR experiments of C8H10 were the main focus of this Article. Pulsed irradiation of C8H10 in the presence of O2((3)Σg(-)) allowed us to determine the kinetics of formation and decay for each of the four components of the O2((1)Δg) EPR signal, which lasted for only a few seconds. We found that the kinetics of EPR-component decay fit nicely to a biexponential kinetics law. The TR EPR 2D spectrum of the third component of the O2((1)Δg) EPR spectrum was examined in experiments using C8H10. This spectrum vividly presents the time evolution of an EPR component. The largest EPR signal and the longest lifetime of O2((1)Δg), τ = 0.4 s, were observed at medium pressure PO2 = 0.4 Torr, T = 293 K. The mechanism of O2((1)Δg) decay in the presence of photosensitizers is discussed. EPR spectra of O2((1)Δg) evidence that the spin-rotational states of O2((1)Δg) are populated according to Boltzmann distribution in the studied time range of 10-100 ms. We believe that this is the first report dealing with the dependence of O2((1)Δg) EPR line width on PO2 and T.

Self-Assembled Benzophenone Bis-urea Macrocycles Facilitate Selective Oxidations by Singlet Oxygen

This manuscript investigates how incorporation of benzophenone, a well-known triplet sensitizer, within a bis-urea macrocycle, which self-assembles into a columnar host, influences its photophysical properties and affects the reactivity of bound guest molecules. We further report the generation of a remarkably stable organic radical. As expected, UV irradiation of the host suspended in oxygenated solvents efficiently generates singlet oxygen similar to the parent benzophenone. In addition, this host can bind guests such as 2-methyl-2-butene and cumene to form stable solid host-guest complexes. Subsequent UV irradiation of these complexes facilitated the selective oxidation of 2-methyl-2-butene into the allylic alcohol, 3-methyl-2-buten-1-ol, at 90% selectivity as well as the selective reaction of cumene to the tertiary alcohol, α,α'-dimethyl benzyl alcohol, at 63% selectivity. However, these products usually arise through radical pathways and are not observed in the presence of benzophenone in solution. In contrast, typical reactions with benzophenone result in the formation of the reactive singlet oxygen that reacts with alkenes to form endoperoxides, diooxetanes, or hydroperoxides, which are not observed in our system. Our results suggest that the confinement, the formation of a stable radical species, and the singlet oxygen photoproduction are responsible for the selective oxidation processes. A greater understanding of the mechanism of this selective oxidation could lead to development of greener oxidants.

Annihilation Limit of a Visible-to-UV Photon Upconversion Composition Ascertained from Transient Absorption Kinetics

Noncoherent sensitized green-to-near-visible upconversion has been achieved utilizing palladium(II) octaethylporphyrin (PdOEP) as the triplet sensitizer and anthracene as the energy acceptor/annihilator in vacuum degassed toluene. Selective 547 nm excitation of PdOEP with incident irradiance as low as 600 μW/cm(2) results in the observation of anthryl fluorescence at higher energy. Stern-Volmer analysis of the dynamic phosphorescence quenching of PdOEP by anthracene possesses an extremely large K(SV) of 810,000 M(-1), yielding a triplet-triplet energy transfer quenching constant of 3.3 × 10(9) M(-1) s(-1). Clear evidence for the subsequent triplet-triplet annihilation (TTA) of anthracene was afforded by numerous experiments, one of the most compelling was an excitation scan illustrating that the Q-band absorption features of PdOEP are solely responsible for sensitizing the anti-Stokes fluorescence. The upconverted emission intensity with respect to the excitation power was shown to vary between quadratic and linear using either coherent or noncoherent light sources, illustrating the expected kinetic limits for the light producing photochemistry under continuous wave illumination. Time-resolved experiments directly comparing the total integrated anthracene intensity/time fluorescence data produced through upconversion (λ(ex) = 547 nm, delayed signal) and with direct excitation (λ(ex) = 355 nm, prompt signal) under conditions where the laser pulse is completely absorbed by the sample reveal annihilation efficiencies of approximately 40%. Similarly, the delayed fluorescence kinetic analysis reported by Schmidt and co-workers (J. Phys. Chem. Lett. 2010, 1, 1795-1799) was used to reveal the maximum possible efficiency from a model red-to-yellow upconverting composition and this treatment was applied to the anthryl triplet absorption decay transients of anthracene measured for the PdOEP/anthracene composition at 430 nm. From this analysis approximately 50% of the anthryl triplets that decay by TTA produce singlet fluorescence, consistent with the notion that annihilation spin statistics does not impose efficiency limits on upconversion photochemistry.

Photochemical Upconversion: A Physical or Inorganic Chemistry Experiment for Undergraduates Using a Conventional Fluorimeter

Photochemical upconversion is a regenerative process that transforms lower-energy photons into higher-energy light through two sequential bimolecular reactions, triplet sensitization of an appropriate acceptor followed by singlet fluorescence producing triplet–triplet annihilation derived from two energized acceptors. This laboratory directly investigates this phenomenon using the facile photo-induced triplet–triplet energy-transfer reaction between the benchmark inorganic chromophore tris(2,2′-bipyridyl)ruthenium(II), [Ru(bpy)3]2+, and 9,10-diphenylanthracene (DPA). Selective green excitation of [Ru(bpy)3]2+ in the presence of DPA results in two observations, the (dynamic) quenching of the [Ru(bpy)3]2+ photoluminescence in the red and the production of upconverted DPA singlet fluorescence in the blue. The quadratic nature of the incident light power dependence for the latter process is easily realized by using the percent transmission characteristics of neutral density filters placed in the excitation beam prior to sample illumination. In a single laboratory period, students are able to directly visualize the upconverted fluorescence generated and gain experience in various aspects of fluorescence spectroscopy, triplet energy-transfer processes, quenching, and reaction molecularity.

Photoalignment Layers for Liquid Crystals from the Di-π-methane Rearrangement

Photoalignment of nematic liquid crystals is demonstrated using a di-π-methane rearrangement of a designed polymer. The alignment mechanism makes use of the strong coupling of the liquid crystal directors to dibenzobarrelene groups. The large structural changes that accompany photoisomerization effectively passivate segments of the polymer, allowing the remaining dibenzobarrelene groups to dominate the director alignment. Photoisomerization requires triplet sensitization, and the polymer was designed to have a uniaxially fixed rigid structure and rapid triplet energy transfer from the proximate benzophenone units to the dibenzobarrelene groups. The isomerization was observed to be regiospecific, and thin films showed alignment.

Supramolecular control during triplet sensitized geometric isomerization of stilbenes encapsulated in a water soluble organic capsule

Triplet sensitized photoisomerization of several stilbenes included within a water-soluble organic capsule has been investigated. In this study octa acid that self assembles in the presence of hydrophobic guest molecules to form a host-guest complex is utilized to solubilize hydrophobic stilbenes and triplet sensitizers in water, and to provide confinement during the geometric isomerization of included olefins. By monitoring the steady state and time resolved room temperature phosphorescence from 4,4'-dimethylbenzil in the presence of acceptor stilbenes and their nitrogen analogues (stilbazole and bispyridyl ethylene) we have been able to establish that triplet-triplet energy transfer occurs between encapsulated donors and encapsulated (or free) acceptors. The mechanism of the energy transfer process is yet to be fully understood although a similar phenomenon has been reported earlier in the literature with Cram's hemicarcerand as the host. The photostationary state composition of cis and trans isomers within the OA capsule is dependent on the relative binding strength of the two isomers with the OA capsule. Further investigation is needed to fully exploit the interesting observations made here to steer the photoisomerization towards a single isomer.

Driving Unidirectional Molecular Rotary Motors with Visible Light by Intra- And Intermolecular Energy Transfer from Palladium Porphyrin

Driving molecular rotary motors using visible light (530-550 nm) instead of UV light was achieved using palladium tetraphenylporphyrin as a triplet sensitizer. Visible light driven rotation was confirmed by UV/vis absorption, circular dichroism and (1)H NMR spectroscopy and the rotation was confirmed to be unidirectional and with similar photostationary states, despite proceeding via a triplet instead of a singlet excited state of the molecular motor. Energy transfer proceeds in both inter- and intramolecular fashion from the triplet state of the porphyrin to the motor. Stern Volmer plots show that the rate of intermolecular quenching of the porphyrin excited state by the molecular motor is diffusion-controlled.

Photophysical properties of dioctyl 4-methoxybenzylidenemalonate: UV-B absorber

Dioctyl 4-methoxybenzylidenemalonate (DOMBM) is an effective stabilizer for photolabile 4-tert-butyl-4'-methoxydibenzoylmethane (BMDBM). DOMBM is superior to the most widely used UV-B absorber, octyl methoxycinnamate (OMC), at preserving its UV-B absorbance in the presence of BMDBM. The energy levels of the lowest excited singlet (S(1)) and triplet (T(1)) states of DOMBM were determined by measuring fluorescence and phosphorescence spectra in ethanol at 77 K. The energy level of the T(1) state of DOMBM is lower than that of BMDBM and is higher than that of OMC. The triplet-triplet energy transfer from BMDBM to DOMBM was demonstrated by measuring the electron paramagnetic resonance (EPR) and time-resolved phosphorescence spectra. The phosphorescence and EPR signals of DOMBM are too weak to be observed through the direct excitation in ethanol at 77 K. The phosphorescence spectrum was observed by using external heavy atom effects of ethyl iodide. The EPR spectrum was observed by using benzophenone as a triplet sensitizer. The fluorescence quantum yield of DOMBM is small in ethanol at room temperature. Only the fast component, due to the heat released from the excited state of DOMBM, was observed in the time-resolved thermal lensing experiments at room temperature. These results show that the quantum yield of the S(1) → T(1) intersystem crossing is negligible and the deactivation process is predominantly internal conversion to the ground state for DOMBM.

Could triplet-sensitised transformation of phenolic compounds represent a source of fulvic-like substances in natural waters?

Here we show that fluorescent compounds that could be classified as “M-like” (marine-like) fulvic acids are formed upon phototransformation of phenol by a triplet sensitiser (anthraquinone-2-sulphonate, AQ2S). The relevant process most likely involves phenol oxidation to phenoxyl radical by triplet AQ2S, followed by dimerisation of phenoxyl radicals into phenoxyphenols and dihydroxybiphenyls. It might be the first step of an oligomerization process that bears resemblance with the expected formation pathways of humic-like substances (HULIS) in the atmosphere. Such a process could account for the formation in surface waters of compounds having similar fluorescence properties as “M-like” fulvic acids. Presently it is thought that such species are formed upon photo-fragmentation of larger humic and fulvic acids (“top-down” pathway), and we propose that an opposite, “bottom-up” pathway could also be operational.

Phototransformation of anthraquinone-2-sulphonate in aqueous solution

Anthraquinone-2-sulphonate (AQ2S) is a triplet sensitiser that has recently been used to model the photoreactivity of chromophoric dissolved organic matter (CDOM). We show that the photolysis quantum yield of AQ2S under UVA irradiation varies from (3.4 ± 0.2) × 10(-3) at μM AQ2S levels to (1.8 ± 0.1) × 10(-2) at 3 mM AQ2S (μ±σ). This trend is consistent with a combination of direct phototransformation and transformation sensitised by a photogenerated reactive species. In both cases a transient water adduct of AQ2S would be involved. Depending on the initial quinone concentration, the adduct could undergo transformation, give back ground-state AQ2S or react with it. The prevalence of the latter process at high AQ2S concentration would account for the increased values of the photolysis quantum yield. When using AQ2S as a triplet sensitiser, one should not exceed an initial concentration of 0.1 mM. Under the latter conditions the sensitised process is negligible compared to the direct photolysis, providing a simpler system to be studied, and the photolysis quantum yield is independent of the initial AQ2S concentration. This paper also shows, by adoption of density functional theory calculations, that the triplet state of AQ2S has most of the spin density localised on C[double bond, length as m-dash]O, analogous to other photoactive quinones, which accounts for the oxidising character of the triplet state that tends to be reduced to a semiquinone radical.

Conformational analysis of 2-anthryl-ethylene derivatives: Photochemical and computational investigation

2-Anthrylethylene derivatives 1 E–5 E and 1 Z are synthesized to study the cis-trans photoisomerization. Interestingly, unlike 9-anthrylethylene derivatives, 2-anthrylethylene derivatives 1 E to 5 E do not exhibit E(trans) to Z (cis) photoisomerization upon direct and triplet sensitization. One-way Z (cis) to E (trans) photoisomerization of 1 Z is found to be very efficient under direct and triplet sensitization conditions, demonstrating the involvement of both singlet and triplet states. 1 E–5 E exhibits excitation wavelength dependent fluorescence indicating the existence of conformers (rotamers) at room temperature, which is confirmed by fluorescence lifetimes measurements of compounds 1 E and 2 E. Theoretical studies are carried out at DFT and ab initio methodology and the calculated relative energy difference of the conformers is very small; it ranges between 2.9 kJ·mol−1 to 6.3 kJ·mol−1 for both ground and excited states.

Tridentate cyclometalated platinum(II) complexes with strong absorption of visible light and long-lived triplet excited states as photosensitizers for triplet–triplet annihilation upconversion

C^N*N cyclometalated platinum(II)L complexes with functionalized acetylide ligands were prepared (L = phenyl, pyrenyl or naphthalimide acetylides). The absorption of the pyrene and naphthalimide derived Pt(II) complexes in the visible region of the spectrum was enhanced relative to the phenylethenyl substituted model complex. Long-lived deep-red emissions were observed for the pyrene (83.7 μs) and naphthalimide (135.7 μs) derived Pt(II) complexes and compared to the phenylethenyl substituted model complex (9.2 μs). Room temperature and 77 K phosphorescence, time-resolved transient absorption and theoretical calculations indicated intraligand triplet excited states for the complexes. The photophysical properties of the complexes were fully rationalized by density functional theory calculations. The complexes were used as triplet photosensitizers for triplet–triplet annihilation based upconversion. Upconversion quantum yields up to 19.5% were observed. These results are useful for design of visible light-harvesting transition metal complexes that shows long-lived triplet excited states. ► Pt(II) acetylide complexes that show strong absorption of visible light were prepared. ► A room temperature long-lived triplet excited state (136 μs) was observed. ► A general strategy of direct metalation of the organic chromophore is proposed. ► The Pt(II) complexes were used as efficient triplet sensitizers for triplet–triplet annihilation upconversion.

Synthesis and Ultrafast Excited-State Dynamics of Zinc and Palladium Triply Fused Diporphyrins

We report the synthesis and ultrafast excited-state dynamics of two new meso-meso, β-β, β-β triply fused diporphyrins, Zn-3DP and Pd-3DP. Both compounds were found to have short excited-state lifetimes: Zn-3DP possessed an average S1 lifetime of 14 ps before nonradiative deactivation to the ground state, whereas Pd-3DP displayed a longer average S1 lifetime of 18 ps before crossing to the T1 state, which itself possessed a very short triplet lifetime of 1.7 ns. The excited-state dynamics of Zn-3DP, compared to similar zinc(II) diporphyrins reported in the literature, suggests that a conical intersection of the S1 and S0 potential energy surfaces plays a major role as a deactivation pathway of these molecules. Furthermore, the short triplet lifetime of Pd-3DP, compared to other diporphyrins that also exploit the intramolecular heavy atom effect, reveals that the position of the heavy atom within the diporphyrin framework influences the strength of spin-orbit coupling. The implications for employing triply fused diporphyrins as NIR-absorbing triplet sensitizers are discussed.

Room temperature long-lived triplet excited state of fluorescein in N^N Pt(II) bisacetylide complex and its applications for triplet–triplet annihilation based upconversions

The room temperature (RT) long-lived triplet excited state of fluorescein was observed in a dbbpy Pt(II) bisfluorescein acetylide complex (Pt-1, where dbbpy = 4,4′-di(tert-butyl)-2,2′-bipyridine). The complex shows strong absorption of visible light (ε = 24,600 M−1 cm−1 at 457 nm). Interestingly, the phosphorescence of the coordination centre is completely quenched and only the fluorescence of ligand was observed for Pt-1 at RT. At 77 K, a phosphorescence band at 667 nm was observed. Spin density analysis and nanosecond time-resolved transient difference absorption spectroscopy proved that the lowest-lying triplet excited state of the complex Pt-1 is localized on the fluorescein acetylide ligand (3IL state), for which the lifetime was determined as 16.4 μs (RT, by the time-resolved transient absorption spectra). The quenching of the 3MLCT phosphorescence in Pt-1 is due to the intramolecular energy transfer of 3MLCT → 3IL. The complex Pt-1 was used as the triplet sensitizer for the triplet–triplet annihilation (TTA) based upconversion. Our results will be useful for preparation of transition metal complexes that show intense absorption of visible light and long-lived triplet excited states, these photophysical properties are useful for applications in photovoltaics, photocatalysis or upconversions, etc.

Efficient Triplet–Triplet Annihilation Upconversion with Platinum(II) Bis(arylacetylide) Complexes That Show Long‐Lived Triplet Excited States

AbstractNN–PtII–bis(acetylide) complexes [NN = 4,4′‐bis(tert‐butyl‐2,2′‐bipyridine) (dbbpy)] with ethynylpyrene (Pt‐2) or 4‐ethynyl‐1,8‐naphthalimide ligands (Pt‐3) that show long‐lived 3IL triplet excited states (τT = 118.0 μs) were used as new triplet sensitizers for triplet–triplet annihilation (TTA) based upconversion (UC). UC quantum yields of up to 18.1 % were observed. We found that the triplet–triplet energy‐transfer (TTET) processes, which are crucial for the TTA UC, were improved by up to 150‐fold and 250‐fold with Pt‐2 (Stern–Volmer quenching constant KSV = 5.70 × 105 M–1) and Pt‐3 (KSV = 9.64 × 105 M–1), respectively, relative to the model complex dbbpy–PtII–bis(phenylacetylide) (Pt‐1) (KSV = 3.80 × 103 M–1). The efficient upconversion is attributed to the long‐lived triplet excited states as well as the high T1‐state energy level of the sensitizers Pt‐2 and Pt‐3.