Effect of Different Substitutions at the 1,7-Bay Positions of Perylenediimide Dyes on Their Optical and Laser Properties.

Perylenediimide (PDI) compounds are widely used as the active units of thin-film organic lasers. Lately, PDIs bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received attention because they provide a way to red-shift the emission with respect to bay-unsubstituted PDIs, while maintaining a good amplified spontaneous emission (ASE) performance at high doping rates. Here, we report the synthesis of a series of six PDI derivatives with different aryloxy groups (PDI 6 to PDI 10) or ethoxy groups (PDI 11) at the 1,7 positions of the PDI core, together with a complete characterization of their optical properties, including absorption, photoluminescence, and ASE. We aim to stablish structure-property relationships that help designing compounds with optimized ASE performance. Film experiments were accomplished at low PDI concentrations in the film, to resemble the isolated molecule behaviour, and at a range of increasing doping rates, to investigate concentration quenching effects. Compounds PDI 10 and PDI 7, bearing substituents in the 2' positions of the benzene ring (the one contiguous to the linking oxygen atom) attached to the 1,7 positions of the PDI core, have shown a better threshold performance, which is attributed to conformational (steric) effects. Films containing PDI 11 show dual ASE.

Panchromatic Light-Capturing Bis-styryl BODIPY-Perylenediimide Donor-Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer.

Invited for the cover of this issue are the groups of Fernando Fernández-Lázaro and Ángela Sastre-Santos at the Universidad Miguel Hernández, Elche, Spain, and Francis D'Souza at the University of North Texas at Denton, Texas, USA. The image depicts the structure and properties of bis-styryl BODIPY-perylenediimide donor-acceptor constructs. Read the full text of the article at 10.1002/chem.202301686.

π-Extended Pyrazinepyrene-Fused Zinc Phthalocyanines: Synthesis and Excited-State Charge Separation Involving Coordinated C60.

A series of pyrazinepyrene-fused zinc phthalocyanines (ZnPc-Pyrn) have been newly synthesized by reacting quinoxaline and the corresponding diamino-functionalized phthalocyanines as a new class of π-extended phthalocyanine systems. Bathochromically shifted absorption as a function of the number of pyrazinepyrene entities due to extended π-conjugation and quenched fluorescence due to the presence of fused pyrazinepyrene were witnessed. The electronic structures of these phthalocyanines were probed by systematic computational and electrochemical studies, while the excited-state properties were examined by pump-probe spectroscopies operating at the femto- and nanosecond time scales. Similar to the excited singlet lifetimes, the excited triplet states also revealed diminished lifetimes with an increased number of pyrazinepyrene entities. Further, the coordinatively unsaturated zinc in these molecules was coordinated with phenyl imidazole-functionalized fullerene, ImC60, to form a new series of donor-acceptor conjugates. Upon full characterization of these conjugates, the occurrence of excited-state charge separation was established by transient pump-probe spectroscopy, covering wide temporal and spatial regions. The lifetime of the final charge-separated states was ∼2 ns and decreased with an increase in the number of fused pyrazinepyrene units.

New Highly Fluorescent Water Soluble Imidazolium-Perylenediimides: Synthesis and Cellular Response.

The synthesis and characterization of two new water soluble 2,6-bis(imidazolylmethyl)-4-methylphenoxy-containing perylenediimides, PDI-1 and PDI-2, are described. These compounds demonstrate a high fluorescence quantum yield in water and were investigated as potential photosensitizers for generating reactive oxygen species with applications in anticancer activities. The HeLa cell line (VPH18) was used to evaluate their efficacy. Fluorescence microscopy was employed to confirm the successful internalization of PDI-1 and PDI-2, while confocal microscopy revealed the specific locations of both PDIs within the lysosomes and mitochondria. In vitro studies were conducted to evaluate the anticancer activity of PDI-1 and PDI-2. Remarkably, these photosensitizers demonstrated a significant ability to selectively eliminate cancer cells when exposed to a specific light wavelength. The water solubility, high fluorescence quantum yield, and selective cytotoxicity of these PDIs toward cancer cells highlight their potential as effective agents for targeted photodynamic therapy. In conclusion, the findings presented here provide a strong foundation for the future exploration and optimization of PDI-1 and PDI-2 as effective photosensitizers in photodynamic therapy, potentially leading to improved treatment strategies for cancer patients.

Tunable J-type aggregation of silicon phthalocyanines in a surface-anchored metal-organic framework thin film.

Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes. The spatial arrangement of the organic linkers can be well-defined in a MOF, and hence optoelectronic functions can be adjusted accordingly. We have used such a strategy to assemble a phthalocyanine chromophore and illustrated that the electronic inter-phthalocyanine coupling can be rationally tuned by introducing bulky side grounds to increase steric hindrance. We have designed new phthalocyanine linkers and using a layer-by-layer liquid-phase epitaxy strategy thin films of phthalocyanine-based MOFs have been fabricated and their photophysical properties explored. It was found that increasing the steric hindrance around the phthalocyanine reduced the effect of J-aggregation in the thin film structures.

Panchromatic Light-Capturing Bis-styryl BODIPY-Perylenediimide Donor-Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer.

Two wide-band-capturing donor-acceptor conjugates featuring bis-styrylBODIPY and perylenediimide (PDI) have been newly synthesized, and the occurrence of ultrafast excitation transfer from the 1 PDI* to BODIPY, and a subsequent electron transfer from the 1 BODIPY* to PDI have been demonstrated. Optical absorption studies revealed panchromatic light capture but offered no evidence of ground-state interactions between the donor and acceptor entities. Steady-state fluorescence and excitation spectral recordings provided evidence of singlet-singlet energy transfer in these dyads, and quenched fluorescence of bis-styrylBODIPY emission in the dyads suggested additional photo-events. The facile oxidation of bis-styrylBODIPY and facile reduction of PDI, establishing their relative roles of electron donor and acceptor, were borne out by electrochemical studies. The electrostatic potential surfaces of the S1 and S2 states, derived from time-dependent DFT calculations, supported excited charge transfer in these dyads. Spectro-electrochemical studies on one-electron-oxidized and one-electron-reduced dyads and the monomeric precursor compounds were also performed in a thin-layer optical cell under corresponding applied potentials. From this study, both bis-styrylBODIPY⋅+ and PDI⋅- could be spectrally characterizes and were subsequently used in characterizing the electron-transfer products. Finally, pump-probe spectral studies were performed in dichlorobenzene under selective PDI and bis-styrylBODIPY excitation to secure energy and electron-transfer evidence. The measured rate constants for energy transfer, kENT , were in the range of 1011  s-1 , while the electron transfer rate constants, kET , were in the range of 1010  s-1 , thus highlighting their potential use in solar energy harvesting and optoelectronic applications.

Development and application of metallo-phthalocyanines as potent G-quadruplex DNA binders and photosensitizers.

Metallo-phthalocyanines (MPc) are common photosensitizers with ideal photophysical and photochemical properties. Also, these molecules have shown to interact with non-canonical nucleic acid structures, such as G-quadruplexes, and modulate oncogenic expression in cancer cells. Herein, we report the synthesis and characterisation of two metallo-phthalocyanines containing either zinc (ZnPc) or nickel (NiPc) in the central aromatic core and four alkyl ammonium lateral chains. The interaction of both molecules with G-quadruplex DNA was assessed by UV-Vis, fluorescence and FRET melting experiments. Both molecules bind strongly to G-quadruplexes and stabilise these structures, being NiPc the most notable G-quadruplex stabiliser. In addition, the photosensitizing ability of both metal complexes was explored by the evaluation of the singlet oxygen generation and their photoactivation in cells. Only ZnPc showed a high singlet oxygen generation either by direct observation or by indirect evaluation using a DPBF dye. The cellular evaluation showed mainly cytoplasmic localization of ZnPc and a decrease of the IC50 values of the cell viability of ZnPc upon light activation of two orders of magnitude. Two metallo-phthalocyanines containing zinc and nickel within the aromatic core have been investigated as G-quadruplex stabilizers and photosensitizers. NiPc shows a high G4 binding but negligible photosensitizing ability while ZnPc exhibits a moderate binding to G-quadruplex together with a high potency to generate singlet oxygen and photocytotoxicity. The interaction with G4s and capacity to be photosensitized is associated with the geometry adopted by the central metal core of the phthalocyanine scaffold.

Simple and Versatile Platforms for Manipulating Light with Matter: Strong Light-Matter Coupling in Fully Solution-Processed Optical Microcavities.

Planar microcavities with strong light-matter coupling, monolithically processed fully from solution, consisting of two polymer-based distributed Bragg reflectors (DBRs) comprising alternating layers of a high-refractive-index titanium oxide hydrate/poly(vinyl alcohol) hybrid material and a low-refractive-index fluorinated polymer are presented. The DBRs enclose a perylene diimide derivative (b-PDI-1) film positioned at the antinode of the optical mode. Strong light-matter coupling is achieved in these structures at the target excitation of the b-PDI-1. Indeed, the energy-dispersion relation (energy vs in-plane wavevector or output angle) in reflectance and the group delay of transmitted light in the microcavities show a clear anti-crossing-an energy gap between two distinct exciton-polariton dispersion branches. The agreement between classical electrodynamic simulations of the microcavity response and the experimental data demonstrates that the entire microcavity stack can be controllably produced as designed. Promisingly, the refractive index of the inorganic/organic hybrid layers used in the microcavity DBRs can be precisely manipulated between values of 1.50 to 2.10. Hence, microcavities with a wide spectral range of optical modes might be designed and produced with straightforward coating methodologies, enabling fine-tuning of the energy and lifetime of the microcavities' optical modes to harness strong light-matter coupling in a wide variety of solution processable active materials.

Disentangling Excimer Emission from Chiral Induction in Nanoscale Helical Silica Scaffolds Bearing Achiral Chromophores.

The synthesis and characterization of diketopyrrolopyrroles and perylenemonoimidodiesters linked to a substituted benzoic acid in the ortho, meta, and para positions, are reported. Grafting of these dyes on the surface of chiral silica nanohelices is used to probe how the morphology of the platform at the mesoscopic level affects the induction of chiroptical properties onto achiral molecular chromophores. The grafted structures are weakly (diketopyrrolopyrroles) or strongly (perylenemonoimidodiesters) emissive, exhibiting both locally-excited state emission and a broad, structureless emission assigned to excimers. The dissymmetry factors obtained using circular dichroism highlight optimized supramolecular organization between the chromophores for enhancing the chiroptical properties of the system. In the ortho- derivatives, poor organization due to steric hindrance is reflected in a low density of chromophores on walls of the silica-nanostructures (<0.1 vs. >0.3 and up to 0.6 molecules/nm2 for the ortho and meta or para derivatives, respectively) and lower gabs values than in the other derivatives (gabs <2×10-5 vs 6×10-5 for the ortho and para derivatives, respectively). The para derivatives presented a better organization and increased values of gabs . All grafted chromophores evidence varying degrees of excimer emission which was not found to directly correlate to their grafting density.

Synthesis of Dipyridylaminoperylenediimide-Metal Complexes and Their Cytotoxicity Studies.

A new family of perylenediimide (PDI) silver and copper complexes has been successfully synthesized by reacting ortho- and bay-substituted (dipyrid-2',2″-ylamino)perylenediimide ligands with metal phosphine fragments. The coordination of the metal center did not reveal a significant effect on the photophysical properties, which are mainly due to the PDI ligands, and in some cases quenching of the luminescence was observed. The antiproliferative effect of the free perylenediimide ligands and the metalloPDI complexes against the cervix cancer cell line HeLa was determined by MTT assay. The free perylenediimide ligands exhibited a moderate cytotoxic activity, but the coordination of silver or copper to the dypyridylamino fragment greatly enhanced the activity, suggesting a synergistic effect between the two fragments. In attempts to elucidate the cellular biodistribution of the PDIs and the complexes, a colocalization experiment using specific dyes for the lysosomes or mitochondria as internal standards revealed a major internalization inside the cell for the metal complexes, as well as a partial mitochondrial localization.

Formation and Photoinduced Electron Transfer in Porphyrin- and Phthalocyanine-Bearing N-Doped Graphene Hybrids Synthesized by Click Chemistry.

Graphene doped with heteroatoms such as nitrogen, boron, and phosphorous by replacing some of the skeletal carbon atoms is emerging as an important class of two-dimensional materials as it offers the much-needed bandgap for optoelectronic applications and provides better access for chemical functionalization at the heteroatom sites. Covalent grafting of photosensitizers onto such doped graphenes makes them extremely useful for light-induced applications. Herein, we report the covalent functionalization of N-doped graphene (NG) with two well-known electron donor photosensitizers, namely, zinc porphyrin (ZnP) and zinc phthalocyanine (ZnPc), using the simple click chemistry approach. Covalent attachment of ZnP and ZnPc at the N-sites of NG in NG-ZnP and NG-ZnPc hybrids was confirmed by using a range of spectroscopic, thermogravimetric and imaging techniques. Ground- and excited-state interactions in NG-ZnP and NG-ZnPc were monitored by using spectral and electrochemical techniques. Efficient quenching of photosensitizer fluorescence in these hybrids was observed, and the relatively easier oxidations of ZnP and ZnPc supported excited-state charge-separation events. Photoinduced charge separation in NG-ZnP and NG-ZnPc hybrids was confirmed by using the ultrafast pump-probe technique. The measured rate constants were of the order of 1010  s,-1 thus indicating ultrafast electron transfer phenomena.

Subphthalocyanine-Diketopyrrolopyrrole Conjugates: 3D Star-Shaped Systems as Non-Fullerene Acceptors in Polymer Solar Cells with High Open-Circuit Voltage.

Invited for this month's cover are the collaborating groups of Prof. Ángela Sastre-Santos, Universidad Miguel Hernández, Prof. Lluis F. Marsal, Universitat Rovira i Virgili and Prof. Tomás Torres, Universidad Autónoma de Madrid, Spain. The cover shows a toy doll holding an umbrella which represents a non-planar, highly conjugated subphthalocyanine-diketopyrrolopyrrole hybrid molecule for non-fullerene organic solar cells. When the sun shines on the umbrella, it absorbs the light, and the doll slides down a polymeric flexible solar cell like a slide, where electrons are produced and electricity flows into the magic wand to illuminate the room. More information can be found in the Full Paper by Ángela Sastre-Santos, Lluis F. Marsal, Tomás Torres, and co-workers.

Efficient charge-transfer from diketopyrrolopyrroles to single-walled carbon nanotubes.

In this contribution, the excited state charge-transfer interactions between single-walled carbon nanotubes (SWCNTs) and a variety of phenyl, 4-bromophenyl, and thiophene substituted diketopyrrolopyrroles (DPPs), is described. Atomic force microscopy (AFM) and aberration corrected high resolution transmission electron microscopy (AC-HRTEM) corroborated the successful formation of DPP/SWCNTs. Steady-state absorption, fluorescence, and Raman spectroscopies all gave insights into the impact on their ground and excited states as well as on the nature of their electronic communication/interaction. Of great value was time-resolved transient absorption spectroscopy on the femto- and nanosecond time-scales; it assisted in deciphering the charge-transfer mechanism from the DPPs to the SWCNT and in analyzing the dynamics thereof with transfer efficiencies of up to 81%. Important confirmation for the one-electron oxidized DPPs came from pulse radiolysis assays with focus on establishing their spectral fingerprints. Our full-fledged work demonstrates that the successful preparation of stable DPP/SWCNTs represents an important step towards establishing them as a viable alternative to porphyrin-based systems in emerging applications such as solar energy conversion.

Subphthalocyanine-Diketopyrrolopyrrole Conjugates: 3D Star-Shaped Systems as Non-Fullerene Acceptors in Polymer Solar Cells with High Open-Circuit Voltage.

Four star-shaped electron acceptors (C1 -OPh, C3 -OPh, C1 -Cl and C3 -Cl) based on a subphthalocyanine core bearing three diketopyrrolopyrrole wings linked by an acetylene bridge have been synthesized. These derivatives feature two different axial substituents (i. e., 4-tert-butylphenoxy (OPh) or chlorine (Cl)) and for each of them, both the C1 and the C3 regioisomers have been investigated. The four compounds exhibit a broad absorption band in the 450-700 nm region, with bandgap values near to 2 eV. These materials were applied in the active layer of inverted bulk-heterojunction polymer solar cells in combination with the donor polymer PBDB-T. Derivatives bearing the OPh axial group showed the best performances, with C1 -OPh being the most promising with a PCE of 3.27 % and a Voc as high as 1.17 V. Despite presenting the widest absorption range, the photovoltaic results obtained with C1 -Cl turned out to be the lowest (PCE=1.01 %).

Phthalocyanine as a Bioinspired Model for Chlorophyll f-Containing Photosystem†II Drives Photosynthesis into the Far-Red Region.

The textbook explanation that P680 pigments are the red limit to drive oxygenic photosynthesis must be reconsidered by the recent discovery that chlorophyll f (Chlf)-containing Photosystem II (PSII) absorbing at 727 nm can drive water oxidation. Two different families of unsymmetrically substituted Zn phthalocyanines (Pc) absorbing in the 700-800 nm spectral window and containing a fused imidazole-phenyl substituent or a fused imidazole-hydroxyphenyl group have been synthetized and characterized as a bioinspired model of the Chlf/TyrosineZ /Histidine190 cofactors of PSII. Transient absorption studies in the presence of an electron acceptor and irradiating in the far-red region evidenced an intramolecular electron transfer process. Visible and FT-IR signatures indicate the formation of a hydrogen-bonded phenoxyl radical in ZnPc II-OH. This study sets the foundation for the utilization of a broader spectral window for multi-electronic catalytic processes with one of the most robust and efficient dyes.

Unveiling the Photoinduced Electron-Donating Character of MoS2 in Covalently Linked Hybrids Featuring Perylenediimide.

The covalent functionalization of MoS2 with a perylenediimide (PDI) is reported and the study is accompanied by detailed characterization of the newly prepared MoS2 -PDI hybrid material. Covalently functionalized MoS2 interfacing organic photoactive species has shown electron and/or energy accepting, energy reflecting or bi-directional electron accepting features. Herein, a rationally designed PDI, unsubstituted at the perylene core to act as electron acceptor, forces MoS2 to fully demonstrate for the first time its electron donor capabilities. The photophysical response of MoS2 -PDI is visualized in an energy-level diagram, while femtosecond transient absorption studies disclose the formation of MoS2 .+ -PDI.- charge separated state. The tunable electronic properties of MoS2 , as a result of covalently linking photoactive organic species with precise characteristics, unlock their potentiality and enable their application in light-harvesting and optoelectronic devices.

Fluorinated Zinc and Copper Phthalocyanines as Efficient Third Components in Ternary Bulk Heterojunction Solar Cells.

Fluorinated zinc and copper metallophthalocyanines MPcF48 are synthesized and incorporated as third component small molecules in ternary organic solar cells (TOSCs). To enable the high performance of TOSCs, maximizing short-circuit current density (J SC) is crucial. Ternary bulk heterojunction blends, consisting of a polymer donor PTB7-Th, fullerene acceptors PC70BM, and a third component MPcF48, are formulated to fabricate TOSCs with a device architecture of ITO/PFN/active layer/V2O5/Ag. Employing copper as metal atom substitution in the third component of TOSCs enhances J SC as a result of complementary absorption spectra in the near-infrared region. In combination with J SC enhancement, suppressed charge recombination, improved exciton dissociation and charge carrier collection efficiency, and better morphology lead to a slightly improved fill factor (FF), resulting in a 7% enhancement of PCE than those of binary OSCs. In addition to the increased PCE, the photostability of TOSCs has also been improved by the appropriate addition of CuPcF48. Detailed studies imply that metal atom substitution in phthalocyanines is an effective way to improve J SC, FF, and thus the performance and photostability of TOSCs.

Perylene-Monoimides: Singlet Fission Down-Conversion Competes with Up-Conversion by Geminate Triplet-Triplet Recombination.

Triplet-excited-state energies of perylene-monoimides (PMIs) lie in the range 1.12 eV ± 2 meV when compared to singlet-excited-state energies of about 2.39 eV ± 2 meV; therefore, the corresponding naphthalene-linked PMI-Dimer was investigated as a novel singlet-fission (SF) material. Ultrafast transient absorption measurements demonstrated the (S1S0)-to-1(T1T1) transformation and the involvement of a mediating step in the overall 1(T1T1) formation. The intermediate is a charge-transfer state that links the initial (S1S0) with the final 1(T1T1), and imposes charge-transfer character on both, which are thus denoted (S1S0)CT and 1(T1T1)CT. At room temperature, the decorrelation and stability of 1(T1T1)CT is affected by the geminate triplet-triplet recombination (G-TTR) of the two triplets. Independent confirmation for G-TTR to afford up-converted (S1S0)UC in fsTA and nsTA measurements with PMI-Dimer, came from probing PMI-Monomer (T1)s in triplet-triplet annihilation up-conversion (TTA-UC). The G-TTR channel, active in the PMI-Dimer at room temperature, is suppressed by working at either low temperatures (∼140 K) or in polar solvents (benzonitrile): Both scenarios assist in stabilizing (T1T1)CT. As a consequence, the triplet quantum yields are 4.2% and 14.9% at room temperature and 140 K, respectively, in 2-methyltetrahydrofuran.

Perylenediimides as more than just non-fullerene acceptors: versatile components in organic, hybrid and perovskite solar cells.

Recent reviews have highlighted the use of perylenediimides (PDIs) as non-fullerene acceptors in bulk-heterojunction organic photovoltaic devices. This review is focused on the advances in the incorporation of PDIs as photoactive components in different solar cell devices. An impressive number of perylenediimides have been incorporated into p-n organic solar cells, as non-fullerene acceptors in bulk heterojunction solar cells, as photosensitisers in dye-sensitised solar cells, in perovskite solar cells, and also as interlayers acting as either electron- or hole-transporting materials. All of this has led to devices with outstanding photovoltaic performance and these are described in this review.

Distance Matters: Effect of the Spacer Length on the Photophysical Properties of Multimodular Perylenediimide-Silicon Phthalocyanine-Fullerene Triads.

A multimodular donor-acceptor conjugate featuring silicon phthalocyanine (SiPc) as the electron donor, and two electron acceptors, namely tetrachloroperylenediimide (PDI) and C60 , placed at the opposite ends of the SiPc axial positions, was newly designed and synthesized, and the results were compared to the earlier reported PDI-SiPc-C60 triad. Minimal intramolecular interactions between the entities was observed. Absorption, fluorescence, computational and electrochemical studies were performed to evaluate the excitation energy, geometry and electronic structure, and energy levels of different photoevents. Steady-state absorption, fluorescence and excitation spectral studies revealed efficient singlet-singlet energy transfer from 1 PDI* to SiPc in the PDI-SiPc dyad and the PDI-SiPc-C60 triad. The measured rates for these photochemical events were found to be much higher than those reported earlier for the triad, due to closer proximity between the PDI and SiPc entities. The distance also affected the charge separation path in which involvement of PDI, and not C60 , in charge separation in the present triad was witnessed. The present investigation brings out the importance of donor-acceptor distances in channeling photochemical events in a multimodular system.