Synergistic Zinc(II) and Formate Doping of Perovskites: Thermal Phase Stabilization of α-FAPbI3 and Enhanced Photoluminescence Lifetime of FA0.8MA0.2PbI3 up to 3.7 µs.

Adding zinc (II) cations and formate anions improves the thermal phase stability of α-FAPbI3 materials, and the spin-coated thin films of such doped FAPbI3 (produced using MACl) show an increased emission lifetime of up to 3.7 µs on quartz (for FA0.8MA0.2PbI3). This work investigates the effects of zinc and formate on the phase stability and time-resolved photoluminescence of FAPbI3 perovskites for solar cell applications. Perovskite samples with varying concentrations of zinc and formate were made by incorporating different amounts of zinc formate and zinc iodide and were characterized with XRD. Doping levels of 1.7% Zn(II) and 1.0% formate (relative to Pb) seem optimal. The thermal phase stability of the doped perovskite powders (FAPbI3) and thin films (FA0.8MA0.2PbI3) was assessed. XRD of the thin films after 6 months shows only the alpha-phase. The time-resolved photoluminescence spectroscopy of the doped spin-coated perovskite samples (FA0.8MA0.2PbI3 produced using MACl) is reported. The results show that synergy between an anionic and a cationic dopant can take place, making the perovskite thermally more phase-stable (not converting to the yellow delta-phase) with a longer charge carrier lifetime. In order to produce good thin films by spin coating, the use of MACl was essential.

Perovskite/silicon tandem solar cells-compositions for improved stability and power conversion efficiency.

Perovskite/Silicon Tandem Solar Cells (PSTSCs) represent an emerging opportunity to compete with industry-standard single junction crystalline silicon (c-Si) solar cells. The maximum power conversion efficiency (PCE) of single junction cells is set by the Shockley-Queisser (SQ) limit (33.7%). However, tandem cells can expand this value to ~ 45% by utilising two stacked solar cells to harvest the solar spectrum more efficiently. 33.9% PCE has already been achieved with PSTSCs. This perspective analyses recent advances in PSTSC technology, with an emphasis on optimal perovskite composition, the problem and mitigation of light-induced halide phase segregation, self-assembled hole transporting monolayers and additives that can improve and stabilise the perovskite. Top-performing compositions show three cationic components (Cs+, FA+, Pb2+) and three anionic (I-, Br-, Cl-) with a bandgap between 1.55 and 1.77 eV and a theoretical maximum of 1.73 eV (717 nm). Anionic additives such as (Br3)- and SCN- reduce trap states and segregation. 2D-perovskite grain boundary interfaces are created with cationic alkylammonium additives such as methyl-phenethylammonium (MPEA) and result in improved performance. 2-, 3- or 4-terminal devices with a (partly) textured silicon heterojunction (SHJ) bottom cell are ideal. An ultra-thin interfacial recombination layer (~ 5 nm) of indium tin oxide (ITO) or indium zinc oxide (IZO) containing a carbazole-based hole transporting self-assembled monolayer (Me-4PACz) is used for optimal 2-terminal tandem devices.

Free base porphyrin-cyanine dye conjugate: synthesis and optical properties.

The covalent combination of a cyanine dye (IR-783) with a tetraphenyl porphyrin unit through an ether linkage results in a photoactive system capable of producing singlet oxygen. The synthesis, characterization and photophysical properties of the resulting novel free base porphyrin-cyanine conjugate named TPPO-IR-783 (TOI) is reported. Excited state properties were studied in various solvents with differing polarity. The fluorescence is strongly solvent dependent, however this is not the case for singlet oxygen phosphorescence, which is only observed in tetrahydrofuran (THF), when comparing 8 different polar, non-polar and medium-polarity solvents. This novel type of porphyrin-cyanine photosensitizer has the ability to produce singlet oxygen and absorbs light at NIR wavelengths.

Metal Coordination Effects on the Photophysics of Dipyrrinato Photosensitizers.

Within this work, we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength, after which, cytotoxic reactive oxygen species (ROS) are generated. The metal coordination allows for the use of the heavy atom effect, which can enhance the triplet generation necessary for generation of ROS. Additionally, the flexibility of these complexes for metal ions, substitutions and ligands allows the possibility to tune their photophysical properties. A general overview of the mechanism of photodynamic therapy and the properties of the triplet photosensitizers is given, followed by further details of dipyrrinato complexes described in the literature that show relevance as photosensitizers for PDT. In particular, the photophysical properties of Re(I), Ru(II), Rh(III), Ir(III), Zn(II), Pd(II), Pt(II), Ni(II), Cu(II), Ga(III), In(III) and Al(III) dipyrrinato complexes are discussed. The potential for future development in the field of (dipyrrinato)metal complexes is addressed, and several new research topics are suggested throughout this work. We propose that significant advances could be made for heteroleptic bis(dipyrrinato)zinc(II) and homoleptic bis(dipyrrinato)palladium(II) complexes and their application as photosensitizers for PDT.

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene-Dimethylaniline.

The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

Structural effects of meso-halogenation on porphyrins.

The use of halogens in the crystal engineering of supramolecular porphyrin assemblies has been a topic of strong interest over the past decades. With this in mind we have characterized a series of direct meso-halogenated porphyrins using single crystal X-ray crystallography. This is accompanied by a detailed conformational analysis of all deposited meso-halogenated porphyrins in the CSD. In this study we have used the Hirshfeld fingerprint plots together with normal-coordinate structural decomposition and determined crystal structures to elucidate the conformation, present intermolecular interactions, and compare respective contacts within the crystalline architectures. Additionally, we have used density functional theory calculations to determine the structure of several halogenated porphyrins. This contrasts conformational analysis with existing X-ray structures and gives a method to characterize samples that are difficult to crystallize. By using the methods outlined above we were able to deduce the impact a meso halogen has on a porphyrin, for example, meso-halogenation is dependent on the type of alternate substituents present when forming supramolecular assemblies. Furthermore, we have designed a method to predict the conformation of halogenated porphyrins, without need of crystallization, using DFT calculations with a high degree of accuracy.

Development of Phenalenone-Triazolium Salt Derivatives for aPDT: Synthesis and Antibacterial Screening.

The increasing number of hospital-acquired infections demand the development of innovative antimicrobial treatments. Antimicrobial photodynamic therapy (aPDT) is a versatile technique which relies on the production of reactive oxygen species (ROS) generated by light-irradiated photosensitizers (PS) in the presence of oxygen (O2). 1H-Phenalen-1-one is a very efficient photosensitizer known for its high singlet oxygen quantum yield and its antimicrobial potential in aPDT when covalently bound to quaternary ammonium groups. Triazolium salts are stable aromatic quaternary ammonium salts that recently appeared as interesting moieties endowed with antimicrobial activities. The coupling between phenalenone and triazolium groups bearing various substituents was realized by copper-catalyzed azide-alkyne cycloaddition followed by alkylation with methyl iodide or 2-(bromomethyl)-1H-phenalen-1-one. As expected, most of the compounds retained the initial singlet oxygen quantum yield, close to unity. Minimum inhibitory concentrations (MIC) of 14 new phenalenone-triazolium salt derivatives and 2 phenalenone-triazole derivatives were determined against 6 bacterial strains (Gram-negatives and Gram-positives species). Most of these PS showed significant photoinactivation activities, the strongest effects being observed against Gram-positive strains with as low as submicromolar MIC values.

Photoinduced and Thermal Single-Electron Transfer to Generate Radicals from Frustrated Lewis Pairs.

Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two-electron processes. However, the detection of radical intermediates indicates that single-electron transfer (SET) generating frustrated radical pairs could also play an important role. These highly reactive radical species typically have significantly higher energy than the FLP, which prompted this investigation into their formation. Herein, we provide evidence that the classical phosphine/borane combinations PMes3 /B(C6 F5 )3 and PtBu3 /B(C6 F5 )3 both form an electron donor-acceptor (charge-transfer) complex that undergoes visible-light-induced SET to form the corresponding highly reactive radical-ion pairs. Subsequently, we show that by tuning the properties of the Lewis acid/base pair, the energy required for SET can be reduced to become thermally accessible.

Making triplets from photo-generated charges: observations, mechanisms and theory.

Triplet formation by charge recombination is a phenomenon that is encountered in many fields of the photo-sciences and can be a detrimental unwanted side effect, but can also be exploited as a useful triplet generation method, for instance in photodynamic therapy. In this Perspective we describe the various aspects that play a role in the decay of charge separated states into local triplet states. The observations and structures of a selection of (pre-2015) molecular electron donor-acceptor systems in which triplet formation by charge recombination occurs are reported. An overview is given of some more recent systems consisting of BODIPY dimers, and BODIPYs attached to various electron-donor units displaying this same triplet formation process. A selection of polymer-fullerene blends in which triplet formation by (non-geminate) charge recombination has been observed, is presented. Furthermore, in-depth information regarding the mechanistic aspects of triplet formation by charge recombination is given on spin dephasing, through hyperfine interactions, as well as on spin-orbit coupling occurring simultaneously with charge recombination. The limits and constraints of these factors and their role in intersystem crossing are discussed. A pictorial view of the two mechanisms is given and this is correlated to aspects of the selection rules for triplet formation, the so-called El-Sayed rules. It is shown that the timescale of triplet formation by charge recombination is indicative for the mechanism that is responsible for the process. The relatively slow rates (CRkT ∼ 1 × 108 s-1 or slower) can be correlated to proton hyperfine interactions (also called the radical pair mechanism), but substantially faster rates (CRkT ∼ 1 × 109 up to 2.5 × 1010 s-1 or faster) have to be correlated to spin-orbit coupling effects. Several examples of molecular systems showing such fast rates are available and their electron donor and acceptor orbitals display an orthogonal relationship with respect to each other. This orientation of (the nodal planes of) the π-orbitals of the donor and acceptor units is correlated to the mechanisms in photodynamic agents and photovoltaic blends.

Tripyridinophane Platform Containing Three Acetate Pendant Arms: An Attractive Structural Entry for the Development of Neutral Eu(III) and Tb(III) Complexes in Aqueous Solution.

We report a detailed characterization of Eu3+ and Tb3+ complexes derived from a tripyridinophane macrocycle bearing three acetate side arms (H3tpptac). Tpptac3- displays an overall basicity (∑ log KiH) of 24.5, provides the formation of mononuclear ML species, and shows a good binding affinity for Ln3+ (log KLnL = 17.5-18.7). These complexes are also thermodynamically stable at physiological pH (pEu = 18.6, pTb = 18.0). It should be noted that the pGd value of Gd-tpptac (18.4) is only slightly lower than that of commercially available MRI contrast agents such as Gd-dota (pGd = 19.2). Moreover, a very good selectivity for these ions over the endogenous cations (log KCuL = 14.4, log KZnL = 12.9, and log KCaL = 9.3) is observed. The X-ray structure of the terbium complex shows the metal coordinated by the nine N6O3 donor set of the ligand and one inner-sphere water molecule. DFT calculations result in two Eu-tpptac structures with similar bond energies (ΔE = 0.145 eV): one structure in which the water is coordinated to the metal ion and one structure in which the water molecule is farther away from the ion, bound to the ligand with an OH-π bond. By detailed luminescence experiments, we demonstrate that the europium complex in aqueous solution presents a hydration equilibrium between nine-coordinate, dehydrated [Eu-tpptac]0 and ten-coordinate, monohydrated [Eu-tpptac(H2O)]0 species. A similar trend is observed for the terbium complex. Despite the presence of this hydration equilibrium, the H3tpptac ligand sensitizes Eu3+ and Tb3+ luminescence efficiently in buffered water at physiological pH. Particularly, the terbium complex displays a long excited-state lifetime of 2.24 ms and an overall quantum yield of 33% with a brightness of 3600 M-1 cm-1. Such features of Ln3+ complexes of H3tpptac indicate that this platform appears to be particularly appealing for the further development of luminescent lanthanide labels.

Air-Stable and Oriented Mixed Lead Halide Perovskite (FA/MA) by the One-Step Deposition Method Using Zinc Iodide and an Alkylammonium Additive.

We present a one-step method to produce air-stable, large-grain mixed cationic lead perovskite films and powders under ambient conditions. The introduction of 2.5 % of Zn(II), confirmed by X-ray diffraction (XRD), results in stable thin films which show the same absorption and crystal structure after 2 weeks of storage under ambient conditions. Next to prolonged stability, the introduction of Zn(II) affects photophysical properties, reducing the bulk defect density, enhancing the photoluminescence (PL), and extending the charge carrier lifetime. Furthermore, 3-chloropropylamine hydrochloride is applied as the film-forming agent. The presence of this amine hydrochloride additive results in highly oriented and large crystal domains showing an ulterior improvement of PL intensity and lifetime. The material can also be prepared as black precursor powder by a solid-solid reaction under ambient conditions and can be pressed into a perovskite pellet. The prolonged stability and the easy fabrication in air makes this material suitable for large-scale, low-cost processing for optoelectronic applications.

Photophysics of perylene monoimide-labelled organocatalysts.

We designed and synthesized cinchona alkaloid derivates PMI-BnCPD, 1 and PMI-dHQD, 2, in which a fluorescent perylene monoimide unit is linked to the quinuclidine fragment. The latter acts as an electron donor, quenching the perylene imide fluorescence in polar solvents. In the organocatalytic application of these compounds, the electron donor is deactivated by binding to an electrophile, e.g. H+. We show that this restores the fluorescence, allowing the compounds to signal the electrophile binding step that occurs in many catalytic reactions. In order to demonstrate that charge transfer is indeed the fluorescence quenching mechanism, we detected the charge separated state by means of transient absorption spectroscopy. Incidentally, the excited state absorption bands of the locally excited and charge transfer states are very similar. The activity of the fluorophore labeled organocatalyst 1 in a fluorogenic Michael addition reaction is demonstrated.

Halogenated earth abundant metalloporphyrins as photostable sensitizers for visible-light-driven water oxidation in a neutral phosphate buffer solution.

Very photostable tetrachloro-metalloporphyrins were developed as sensitizers for visible-light-driven water oxidation coupled to cobalt based water-oxidation catalysts in concentrated (0.1 M) phosphate buffer solution. Potassium persulfate (K2S2O8) acts as a sacrificial electron acceptor to oxidize the metalloporphyrin photosensitizers in their excited states. The radical cations thus produced drive the cobalt based water-oxidation catalysts: Co4O4-cubane and Co(NO3)2 as pre-catalyst for cobalt-oxide (CoOx) nanoparticles. Two different metalloporphyrins (Cu(ii) and Ni(ii)) both showed very high photostability in the photocatalytic reaction, as compared to non-halogenated analogues. This indicates that photostability primarily depends on the substitution of the porphyrin macrocycle, not on the central metal. Furthermore, our molecular design strategy not only positively increases the electrochemical potential by 120-140 mV but also extends the absorption spectrum up to ∼600 nm. As a result, the solar photon capturing abilities of halogenated metalloporphyrins (Cu(ii) and Ni(ii)) are comparable to that of the natural photosynthetic pigment, chlorophyll a. We successfully demonstrate long-term (>3 h) visible-light-driven water oxidation using our molecular system based on earth-abundant (first-row transition) metals in concentrated phosphate buffer solution.

Robust Benzo[g, h, i]perylenetriimide Dye-Sensitized Electrodes in Air-Saturated Aqueous Buffer Solution.

Highly electron deficient benzo[ghi]perylenetriimide (BPTI) chromophores were persistently anchored to a metal oxide electrode surface and reversible formation of their radical anions was shown in air-saturated aqueous buffer solution. Our results show a very low reaction-rate constant of BPTI(.-) with O2 (k=1.92 ± 0.05 × 10(-2) s(-1)). BPTI is a robust chromophore that can be used as the electron acceptor in molecule-based artificial photosynthetic devices for direct water splitting in aqueous phase.

Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis.

A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300-500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered =-0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2 O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2 =39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10(-2) ∼10(-1) cm(2) V(-1) s(-1)) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells.

Photoinduced charge transport over branched conjugation pathways: donor-acceptor substituted 1,1-diphenylethene and 2,3-diphenylbutadiene.

Photoinduced charge transport in 1,1-diphenylethene and 2,3-diphenylbutadiene functionalized with an electron donating dimethylamino group and an electron accepting cyano group is reported. UV-spectroscopy reveals that in these compounds, which incorporate a cross-conjugated spacer, a direct charge transfer transition is possible. It is shown by application of the generalized Mulliken-Hush approach that introduction of an additional branching point in the π-electron spacer (i.e., when going from the 1,1-diphenylethene to the 2,3-diphenylbutadiene) leads to only a moderate reduction (68-92%) of the electronic coupling between the ground and the charge separated state. The σ-electron system is however likely to be dominant in the photoinduced charge separation process.

Triplet formation by charge recombination in thin film blends of perylene red and pyrene: developing a target model for the photophysics of organic photovoltaic materials.

Photoinduced charge separation in a mixture of Perylene Red (N,N'-bis(2,6-di-isopropylphenyl)-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic acid bis-imide) and pyrene, organized in thin solid film on quartz, was studied by means of steady-state absorption and emission spectroscopy and by femtosecond transient absorption spectroscopy. Steady state spectroscopy shows substantial interaction between the two chromophores in the ground and excited states. Luminescence quenching indicates charge transfer interaction. Global and target analysis of the transient absorption data indicates a complex photophysical behavior with the formation of long-lived charges (free charge carriers) and of a triplet excited state species (with rates of ∼10.4 × 10(9) and 72.1 × 10(6) s(-1)) via charge recombination pathways from charged states. A generally applicable target model for the analysis of photophysical data of photovoltaic blends is developed.

Decoupling fluorescence and photochromism in bifunctional azo derivatives for bulk emissive structures.

Bifunctional molecules that combine independent push-pull fluorophores and azo photochromes have been synthesized to create fluorescent structures upon light-induced migration in neat thin films. Their photochromic and emissive properties have been systematically investigated and interpreted in light of those of the corresponding model compounds. Fluorescence lifetimes and photoisomerization and fluorescence quantum yields have been determined in toluene solution. Kinetic analyses of the femtosecond transient absorption spectra reveal that the fluorophores evolve in a few picoseconds into a distorted intramolecular charge-transfer excited state, strongly stabilized in energy. Radiative relaxation to the ground state occurred competitively with the energy-transfer process to the azo moiety. Introduction of a 10 Å-long rigid and nonconjugated bridge between the photoactive units efficiently inhibits the energy transfer while it imparts enhanced free volume, which favors photoactivated molecular migration in the solid state.

Bis-semiquinone (bi-radical) formation by photoinduced proton coupled electron transfer in covalently linked catechol-quinone systems: Aviram's hemiquinones revisited.

The structure and reactivity of a covalently linked catechol-ortho-benzoquinone (hemiquinone) is studied by UV-Vis and IR absorption spectroscopy. Nanosecond transient absorption spectroscopy of the hemiquinone reveals the formation of bi-radical state consisting of two semiquinone units. It is a long-lived state resulting from proton coupled electron transfer (PCET).