Best practice in determining key photophysical parameters in triplet–triplet annihilation photon upconversion

Triplet–triplet annihilation photon upconversion (TTA-UC) is a process in which low-energy light is transformed into light of higher energy. During the last two decades, it has gained increasing attention due to its potential in, e.g., biological applications and solar energy conversion. The highest efficiencies for TTA-UC systems have been achieved in liquid solution, owing to that several of the intermediate steps require close contact between the interacting species, something that is more easily achieved in diffusion-controlled environments. There is a good understanding of the kinetics dictating the performance in liquid TTA-UC systems, but so far, the community lacks cohesiveness in terms of how several important parameters are best determined experimentally. In this perspective, we discuss and present a “best practice” for the determination of several critical parameters in TTA-UC, namely triplet excited state energies, rate constants for triplet–triplet annihilation (kTTA), triplet excited-state lifetimes (τT), and excitation threshold intensity (Ith). Finally, we introduce a newly developed method by which kTTA, τT, and Ith may be determined simultaneously using the same set of time-resolved emission measurements. The experiment can be performed with a simple experimental setup, be ran under mild excitation conditions, and entirely circumvents the need for more challenging nanosecond transient absorption measurements, a technique that previously has been required to extract kTTA. Our hope is that the discussions and methodologies presented herein will aid the photon upconversion community in performing more efficient and manageable experiments while maintaining—and sometimes increasing—the accuracy and validity of the extracted parameters

Kinetics and Efficiency of Triplet-Triplet Annihilation Photon Upconversion under Pulsed Excitation Conditions

Triplet-triplet annihilation is a promising method to convert low energy photons to high energy ones. Due to the long time-scales and the bimolecular nature of the process, the overall efficiency of triplet-triplet annihilation greatly depends on the excitation type and intensity. Upconversion efficiencies are usually measured using continuous wave conditions. Here we develop an analytical and experimental method to investigate how the excitation modulation affects the triplet-triplet annihilation efficiency. The simulated and experimental results demonstrate high consistency. The triplet-triplet annihilation efficiency drops as expected with increasing excitation frequency at a fixed average power density, which our simulations accurately predicts. The method described here allows to relate efficiencies measured at pulsed conditions with those measured at continuous wave conditions

Temperature and viscosity dependence of the triplet energy transfer process in porphyrin dimers

The temperature and viscosity dependence of the triplet energy transfer (TET) process in porphyrin dimers has been studied. A zinc porphyrin (donor) and a free base porphyrin (acceptor) are covalently linked together by rigid bridging chromophores at a center-center distance of 25 Angstrom. Due to the large donor-acceptor distance and the weakness of the spin forbidden transitions involved, neither direct (through space) electron exchange nor Coulombic mechanisms are expected to contribute to the observed TET process. The results from transient absorption measurements at temperatures between room temperature and 80 K show that TET occurs with unexpectedly high efficiency in the systems connected by fully conjugated bridges and a pronounced temperature dependence of the process is observed. Comparison of the TET efficiencies in dimers connected by different bridging chromophores correlates well with a transfer reaction governed by a through bond exchange (superexchange) interaction. However, in high viscosity media the TET process is dramatically slowed down. This is attributed to a conformational gating of the TET process where the electronic coupling varies strongly with the relative orientation of the donor and the bridging chromophore. Further, the zinc porphyrin donor offers two distinct donor species, T-1A and T-1B. At room temperature, the TET rate constant of the T-1A Species is about two orders of magnitude larger than for the T-1B species. The dimers studied are well suited model systems for materials where the rate of the transfer reactions can be changed by external stimuli

Photophysical and structural properties of the fluorescent nucleobase analogues of the tricyclic cytosine (tC) family

Fundamental insight into the unique fluorescence and nucleobase-mimicking properties of the fluorescent nucleobase analogues of the tC family is not only vital in explaining the behaviour of these probes in nucleic acid environments, but will also be profitable in the development of new and improved fluorescent base analogues. Here, temperature-dependent fluorescence quantum yield measurements are used to successfully separate and quantify the temperature-dependent and temperature-independent non-radiative excited-state decay processes of the three nucleobase analogues tC, tC(O) and tC(nitro); all of which are derivatives of a phenothiazine or phenoxazine tricyclic framework. These results strongly suggest that the non-radiative decay process dominating the fast deactivation of tCnitro is an internal conversion of a different origin than the decay pathways of tC and tC(O). tCnitro is reported to be fluorescent only in less dipolar solvents at room temperature, which is explained by an increase in excited-state dipole moment along the main non-radiative decay pathway, a suggestion that applies in the photophysical discussion of large polycyclic nitroaromatics in general. New insight into the ground and excited-state potential energy surfaces of the isolated tC bases is obtained by means of high level DFT and TDDFT calculations. The S-0 potential energy surfaces of tC and tCnitro possess two global minima corresponding to geometries folded along the middle sulfur-nitrogen axis separated by an energy barrier of 0.05 eV as calculated at the B3LYP/6-311 + G(2d, p) level. The ground-state potential energy surface of tC(O) is also predicted to be shallow along the bending coordinate but with an equilibrium geometry corresponding to the planar conformation of the tricyclic framework, which may explain some of the dissimilar properties of tC and tC(O) in various confined (biological) environments. The S-1 equilibrium geometries of all three base analogues are predicted to be planar. These results are discussed in the context of the tC bases positioned in double-stranded DNA scenarios

Intersystem Crossing versus Electron Transfer in Porphyrin-Based Donor−Bridge−Acceptor Systems: Influence of a Paramagnetic Species

We have investigated how the spin state of an acceptor influences the photophysical processes in a donor−bridge−acceptor (D−B−A) system. The system of choice has zinc porphyrin as the electron donor and high- or low-spin iron(III) porphyrin as the acceptor. The spin state of the acceptor porphyrin is switched simply by coordinating imidazole ligands to the metal center. The D−A center−center distance is 26 Å, and the bridging chromophore varies from π-conjugated to a σ-bonded system. The presence of a high-spin iron(III) porphyrin in such systems has previously been shown to significantly enhance intersystem crossing in the remote zinc porphyrin donor, whereas no significant electron transfer to the iron porphyrin acceptor was observed, even though the thermodynamics would allow for photoinduced electron transfer. Here, we demonstrate that by switching the acceptor to a low-spin state, the dominating photophysical process is drastically changed; the low-spin system shows long-range electron transfer on the picosecond time-scale, and intersystem crossing occurs at its “normal” rate

Characterization of Nucleobase Analogue FRET Acceptor tC(nitro)

The fluorescent nucleobase analogues of the tricyclic cytosine (tC) family, tC and tC(O), possess high fluorescence quantum yields and single fluorescence lifetimes, even after incorporation into double-stranded DNA, which make these base analogues particularly useful as fluorescence resonance energy transfer (FRET) probes. Recently, we reported the first all-nucleobase FRET pair consisting of tC(O) as the donor and the novel tC(nitro) as the acceptor. The rigid and well-defined position of this FRET pair inside the DNA double helix, and consequently excellent control of the orientation factor in the FRET efficiency, are very promising features for future studies of nucleic acid structures. Here, we provide the necessary spectroscopic and photophysical characterization Of tC(nitro) needed in order to utilize this probe as a FRET acceptor in nucleic acids. The lowest energy absorption band from 375 to 525 nm is shown to be the result of a single in-plane polarized electronic transition oriented similar to 27 degrees from the molecular long axis, This band overlaps the emission bands of both tC and tC(O), and the Forster characteristics of these donor-acceptor pairs are calculated for double-stranded DNA scenarios. In addition, the UV-vis absorption of tC(nitro) is monitored in a broad pH range and the neutral form is found to be totally predominant under physiological conditions with a pK(a) of 11.1. The structure and electronic spectrum Of tC(nitro) is further characterized by density functional theory calculations

Photon upconversion facilitated molecular solar energy storage

Photon upconversion is used to facilitate the production of a solar fuel. This is done by collocating a triplet–triplet annihilation upconversion system in a microfluidic device with a molecular solar thermal energy storage system. Incoherent truncated white light is used to drive the reaction and the green part of the spectrum is upconverted to blue light, which in turn is absorbed by the solar fuel

A general approach for all-visible-light switching of diarylethenes through triplet sensitization using semiconducting nanocrystals

Coupling semiconducting nanocrystals (NCs) with organic molecules provides an efficient route to generate and transfer triplet excitons. These excitons can be used to power photochemical transformations such as photoisomerization reactions using low energy radiation. Thus, it is desirable to develop a general approach that can efficiently be used to control photoswitches using all-visible-light aiming at future applications in life- and materials sciences. Here, we demonstrate a simple \u27cocktail\u27 strategy that can achieve all-visible-light switchable diarylethenes (DAEs) through triplet energy transfer from the hybrid of CdS NCs and phenanthrene-3-carboxylic acid, with high photoisomerization efficiency and improved fatigue resistance. The size-tunable excitation energies of CdS NCs make it possible to precisely match the clear spectral window of the relevant DAE photoswitch. We demonstrate reversible all-visible-light photoisomerization of a series of DAE derivatives both in the liquid and solid state, even in the presence of oxygen. Our general strategy is promising for fabrication of all-visible-light activated optoelectronic devices as well as memories, and should in principle be adaptable to photopharmacology

A general approach for all-visible-light switching of diarylethenes through triplet sensitization using semiconducting nanocrystals

Coupling semiconducting nanocrystals (NCs) with organic molecules provides an efficient route to generate and transfer triplet excitons. These excitons can be used to power photochemical transformations such as photoisomerization reactions using low energy radiation. Thus, it is desirable to develop a general approach that can efficiently be used to control photoswitches using all-visible-light aiming at future applications in life- and materials sciences. Here, we demonstrate a simple ‘cocktail’ strategy that can achieve all-visible-light switchable diarylethenes (DAEs) through triplet energy transfer from the hybrid of CdS NCs and phenanthrene-3-carboxylic acid, with high photoisomerization efficiency and improved fatigue resistance. The size-tunable excitation energies of CdS NCs make it possible to precisely match the clear spectral window of the relevant DAE photoswitch. We demonstrate reversible all-visible-light photoisomerization of a series of DAE derivatives both in the liquid and solid state, even in the presence of oxygen. Our general strategy is promising for fabrication of all-visible-light activated optoelectronic devices as well as memories, and should in principle be adaptable to photopharmacology

Efficient Visible‐to‐UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4\ua0eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting