No abstract

In the present study, the red-light absorbing platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP) was used as a triplet sensitizer in conjunction with two distinct iodophenyl-bearing BODIPY derivatives independently serving as triplet acceptors/annihilators poised for photon upconversion based on triplet-triplet annihilation. In deaerated benzene solutions, extremely stable and high quantum efficiency green (Phi(UC) = 0.0313 +/- 0.0005) and yellow (Phi(UC) = 0.0753 +/- 0.0036) upconverted emissions were observed from selective red excitation of the PtTPBP sensitizer at 635 +/- 5 nm. The current systems represent the first examples of photon upconversion where aromatic hydrocarbons do not serve the role of triplet acceptor/annihilator. Notably, the nature of the current chromophore compositions permitted highly reproducible upconversion quantum efficiency determinations while permitting the evaluation of the triplet-triplet annihilation quantum yields in both instances.

Abstract:The upconverting properties of a dye cocktail composed of palladium(II) octaethylporphyrin (PdOEP, triplet sensitizer) and 9,10-diphenylanthracene (DPA, triplet acceptor/annihilator) were investigated as a function of temperature in several low glass transition temperature (T g ) polymer hosts including an ethyleneoxide-epichlorohydrin copolymer (EO-EPI) and the polyurethanes Texin 270, Texin 285, and Tecoflex EG-80A. Selective excitation of PdOEP at 544 nm in the presence of DPA in these materials resulted in anti-Stokes blue emission from DPA, a consequence of sensitized triplet-triplet annihilation (TTA) photochemistry, confirmed by the quadratic dependence of the upconverted fluorescence intensity with respect to incident light power. The upconversion process was completely suppressed by cooling a PdOEP/DPA blend film to below the T g of the respective polymer. However, the blue emission was clearly visible by the naked eye upon heating these films to room temperature (290 K). Subsequently, the upconverted emission intensity increased with increasing temperature and was found to be completely reversible upon several heating and cooling cycles provided the temperature remained below 400 K. Heating samples above this temperature resulted in unrecoverable failure of the material to produce upconverted photons. The phosphorescence intensity decay of PdOEP in the polymer host, Tecoflex EG-80A, adequately fits to a sum of two exponential functions as well as the Kohlrausch-Williams-Watts (KWW) stretched exponential model. Increasing the temperature of the film increases the complexity and heterogeneity of the system as evidenced by the lower values obtained from the KWW model as the temperature increases.

Upconverted yellow singlet fluorescence from rubrene (5,6,11,12-tetraphenylnapthacene) was generated from selective excitation (lambdaex = 725 nm) of the red light absorbing triplet sensitizer palladium(II) octabutoxyphthalocyanine, PdPc(OBu)8, in vacuum degassed toluene solutions using a Nd:YAG/OPO laser system in concert with gated iCCD detection. The data are consistent with upconversion proceeding from triplet-triplet annihilation (TTA) of rubrene acceptor molecules. The TTA process was confirmed by the quadratic dependence of the upconverted delayed fluorescence intensity with respect to incident light, measured by integrating the corresponding kinetic traces as a function of the incident excitation power. In vacuum degassed toluene solutions, the red-to-yellow upconversion process is stable under continuous long wavelength irradiation and is readily visualized by the naked eye even at modest laser fluence (0.6 mJ/pulse). In aerated solutions, however, selective excitation of the phthalocyanine sensitizer leads to rapid decomposition of rubrene into its corresponding endoperoxide as evidenced by UV-vis (in toluene), 1H NMR (in d6-benzene), and MALDI-TOF mass spectrometry, consistent with the established reactivity of rubrene with singlet dioxygen. The upconversion process in this triplet sensitizer/acceptor-annihilator combination was preliminarily investigated in solid polymer films composed of a 50:50 mixture of an ethyleneoxide/epichlorohydrin copolymer, P(EO/EP). Films that were prepared under an argon atmosphere and maintained under this inert environment successfully achieve the anticipated quadratic incident power dependence, whereas air exposure causes the film to deviate somewhat from this dependence. To the best of our knowledge, the current study represents the first example of photon upconversion using a phthalocyanine triplet sensitizer, furthering the notion that anti-Stokes light-producing sensitized TTA appears to be a general phenomenon as long as proper energy criteria are met.

Low power visible-to-UV photon upconversion is demonstrated for the first time, achieved from two simple organic chromophores dissolved in benzene. Selective 442 nm excitation of the triplet sensitizer 2,3-butanedione (biacetyl) in the presence of the laser dye 2,5-diphenyloxazole (PPO) results in the observation of singlet fluorescence from the latter in the UV centered at 360 nm, anti-Stokes shifted by a record 0.64 eV with respect to the excitation. All of the experimental data are consistent with the upconverted singlet PPO fluorescence being produced as a result of biacetyl-sensitized triplet-triplet annihilation (TTA) of triplet excited PPO chromophores. Nanosecond laser flash photolysis performed under pseudo-first-order conditions revealed the bimolecular rate constant of triplet-triplet energy transfer between the biacetyl sensitizer and PPO acceptor, k(q) = 9.0 x 10(8) M(-1)s(-1). The TTA process was confirmed by the quadratic dependence of the upconverted integrated PPO emission intensity measured with respect to incident 442 nm light power density. The maximum quantum yield of the upconverted emission (0.0058 +/- 0.0002) was determined relative to 1,8-diphenyl-1,3,5,7-octatetraene, both measured with 0.389 W/cm(2) incident power density. The PPO triplet-triplet annihilation rate constant (k(TT)) was determined from transient absorption decays monitored at the peak of its characteristic triplet-to-triplet excited-state absorption (500 nm) as a function of incident pulsed laser fluence; this process attains the diffusion limit in benzene at room temperature, k(TT) = 1.1 +/- 0.1 x 10(10) M(-1) s(-1).

Sensitized red-to-blue upconversion with a record 0.8 eV anti-Stokes shift has been achieved utilizing platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP) as the triplet sensitizer and perylene as the energy acceptor/annihilator in deaerated benzene. Selective 635 nm excitation of PtTPBP results in the observation of perylene fluorescence centered at 451 nm. Stern-Volmer analysis of dynamic phosphorescence quenching of PtTPBP by perylene yields a triplettriplet energy transfer quenching constant of 4.08 Â 10 9 M -1 s -1 . Clear evidence for the subsequent triplet-triplet annihilation of 3 perylene* was afforded by the quadratic dependence of the integrated perylene fluorescence spectra with respect to incident 635 nm light power. The maximum upconversion quantum yield of perylene fluorescence under our sensitized excitation conditions is 0.0065 ( 0.0001, as ascertained by relative actinometry. The present chromophore combination was successfully translated into the solid state using a low glass transition temperature polyurethane host polymer, which produced upconverted photons for months when stored under ambient conditions.

Selective near-IR (NIR) excitation (780 nm) of the conjugated supermolecule ruthenium(II) [15-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-bis[(5,5',-10,20-di(2',6'-bis(3,3-dimethylbutoxy)phenyl)porphinato)zinc(II)]ethyne][4'-pyrrolidin-1-yl-2,2';6',2''-terpyridine] bis(hexafluorophosphate) (Pyr(1)RuPZn(2)) in solutions containing N,N-bis(ethylpropyl)perylene-3,4,9,10-tetracarboxylicdiimide (PDI) or tetracene gives rise to a substantial anti-Stokes energy gain (PDI, 0.70 eV; tetracene, 0.86 eV). Experimental data clearly demonstrate that this upconverted fluorescence signal is produced via Pyr(1)RuPZn(2)-sensitized triplet-triplet annihilation (TTA) photochemistry. The TTA process was confirmed by the quadratic dependence of the integrated (1)PDI* emission centered at 541 nm derived from 780 nm laser excitation. The T(1)→T(n) excited state absorption decay of Pyr(1)RuPZn(2), monitored at 900 nm as a function of PDI concentration, revealed Stern-Volmer and bimolecular quenching constants of 10 048 M(-1) and 5.9 × 10(8) M(-1) s(-1), respectively, for the PDI triplet sensitization process. The T(1)→T(n) PDI extinction coefficient at 560 nm (ε(T) = 6.6 × 10(4) M(-1) cm(-1)) was determined through the triplet energy transfer method utilizing anthracene as the donor chromophore. (3)PDI* transient triplet absorption dynamics observed as a function of 485 nm incident nanosecond pump laser fluence demonstrate a bimolecular (3)PDI*-(3)PDI* TTA rate constant (k(TT) = 1.0 ± 0.2 × 10(9) M(-1) s(-1)). The maximum quantum yield of the supermolecule-sensitized PDI upconverted emission (Φ(UC) = 0.0075 ± 0.0002) was determined relative to [Os(phen)(3)][PF(6)](2) at an incident laser power of 22 mW at 780 nm. This study successfully demonstrates NIR-to-visible photon upconversion and achieves a new record anti-Stokes shift of 0.86 eV for sensitized TTA, using the supermolecular Pyr(1)RuPZn(2)sensitizer. The stability of the Pyr(1)RuPZn(2)/PDI chromophore combination is readily apparent as continuous irradiation at 780 nm produces 541 nm centered fluorescence with no significant decrease in intensity measured over time domains exceeding several hours. The molecular components of these NIR-to-vis upconverting compositions illustrate that substantial anti-Stokes energy gains via a TTA process can be effortlessly realized.

Blue-green upconverted emission from 2-chloro-bis-phenylethynylanthracene (2CBPEA) sensitized by the red-absorbing platinum(II)tetraphenyltetrabenzoporphyrin (PtTPBP) has been investigated in N,N-dimethylformamide (DMF). The upconverted singlet fluorescence of 2CBPEA resulting from its sensitized triplet-triplet annihilation (TTA) is observed following selective excitation of PtTPBP at 635 +/- 5 nm. Stern-Volmer analysis of the photoluminescence quenching of PtTPBP by 2CBPEA yields a bimolecular quenching constant of 1.62 x 10(9) M(-1) s(-1), slightly below the diffusion limit in DMF at room temperature. The TTA process was confirmed by the quadratic dependence of the integrated upconverted singlet fluorescence emission profile of 2CBPEA measured as a function of 635 nm incident laser power. Time-resolved emission spectra following 630 nm nanosecond laser pulses illustrate the prompt nature of porphyrin phosphorescence quenching and the delayed nature of the upconverted singlet fluorescence from 2CBPEA. Transient absorption decays monitored at the peak of the characteristic 2CBPEA triplet-triplet excited-state absorption (490 nm) measured as a function of incident nanosecond 630 nm pump laser fluence recovered the rate constant for the sensitized TTA process, k(TT) = 5.64 +/- 0.08 x 10(9) M(-1) s(-1). To calculate this rate constant, we determined the triplet-triplet extinction coefficient of 2CBPEA (12,500 M(-1) cm(-1) at 490 nm) utilizing triplet energy transfer from donors with known excited-state extinction coefficients, namely [Ru(bpy)(3)](2+) and 2-acetonaphthone and averaged these values. The current work, to the best of our knowledge, represents the first example of red-to-blue upconversion thus demonstrating another viable sensitized TTA process, as well as providing the first measurements of k(TT) in a photon upconverting scheme. As 2CBPEA is stable under ambient conditions, this chromophore represents an almost ideal candidate for light-producing sensitized TTA in aerated polymeric materials, and we demonstrate successful translation of the present donor-acceptor/annihilator system into a low T(g) polyurethane.