Carbon nanotube heterogenization improves cobalt pyridyldiimine complex CO2 reduction activity in aqueous carbonate buffer.

We present two novel cobalt pyridyldiimine complexes functionalized with pyrene. Initially modest in homogeneous acetonitrile solution, their electrocatalytic CO2 reduction performance significantly improves upon immobilization on MWCNTs in an aqueous carbonate buffer. The complexes exhibit outstanding stability, with CO selectivity exceeding 97%, and TON and TOF values reaching up to 104 and above 1.2 s-1, respectively.

Exceptional anticancer photodynamic properties of [1,4-Bis(3,6,9,12-Tetraoxatridec-1-yloxy)phthalocyaninato]zinc(II).

Phthalocyanines have been described as effective photosensitizers for photodynamic therapy and are therefore, being studied for their biomedical applications. The metalation of photosensitizers can improve their photodynamic therapy potential. Here, we focus on the biological properties of [1,4-Bis(3,6,9,12-Tetraoxatridec-1-yloxy)phthalocyaninato]zinc(II) (ZnPc(αEG4)2) and demonstrate its exceptional anticancer activity upon light stimulation to kill preferentially cancer cells with a start of efficiency at 10 pM. Indeed, in this work we highlighted the high selectivity of ZnPc(αEG4)2 for cancer cells compared with healthy ones and we establish its mechanism of action, enabling us to conclude that ZnPc(αEG4)2 could be a powerful tool for cancer therapy.

Antenna Effect in Noble Metal-Free Dye-Sensitized Photocatalytic Systems Enhances CO2 -to-CO Conversion.

Dye-sensitized photocatalytic systems (DSPs) have been extensively investigated for solar-driven hydrogen (H2 ) evolution. However, their application in carbon dioxide (CO2 ) reduction remains limited. Furthermore, current solar-driven CO2 -to-CO DSPs typically employ rhenium complexes as catalysts. In this study, we have developed DSPs that incorporate noble metal-free components, specifically a zinc-porphyrin as photosensitizer (PS) and a cobalt-quaterpyridine as catalyst (CAT). Taking a significant stride forward, we have achieved an antenna effect for the first time in CO2 -to-CO DSPs by introducing a Bodipy as an additional chromophore to enhance light harvesting efficiency. The energy transfer from Bodipy to zinc porphyrin resulted in remarkable stability (turn over number (TON)=759 vs. CAT), and high CO evolution activity (42 mmol g-1 h-1 vs. CAT).

Dye-Sensitized Photocatalysis: Hydrogen Evolution and Alcohol-to-Aldehyde Oxidation without Sacrifical Electron Donor.

There is a growing interest in developing dye-sensitized photocatalytic systems (DSPs) to produce molecular hydrogen (H2 ) as alternative energy source. To improve the sustainability of this technology, we replaced the sacrificial electron donor (SED), typically an expensive and polluting chemical, with an alcohol oxidation catalyst. This study demonstrates the first dye-sensitized system using a diketopyrrolopyrrole dye covalently linked to 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) based catalyst for simultaneous H2 evolution and alcohol-to-aldehyde transformation operating in water with visible irradiation.

Exploring the Impact of Successive Redox Events in Thin Films of Metal-Organic Frameworks: An Absorptiometric Approach.

Metal-organic frameworks (MOFs) featuring redox activity are highly appealing for electrocatalytic or charge accumulation applications. An important aspect in this field is the ability to address as many redox centers as possible in the material by an efficient diffusion of charges. Herein, we investigate for the first time the charge diffusion processes occurring upon two sequential one-electron reductions in an MOF thin film. Two pyrazolate-zinc(II)-based MOFs including highly electro-deficient perylene diimide (PDI) ligands were grown on conducting substrates, affording thin films with double n-type electrochromic properties as characterized by spectroelectrochemical analysis. In depth electrochemical and chronoabsorptiometric investigations were carried out to probe the charge diffusion in the MOF layers and highlighted significant differences in terms of diffusion kinetics and material stability between the first and second successive reduction of the redox-active PDI linkers. Our results show that MOFs based on multiredox centers are more sensitive to encumbrance-related issues than their monoredox analogues in the context of electrochemical applications, an observation that further underlines the fundamental aspect of careful pore dimensions toward efficient and fast ion diffusion.

Development of targeted photodynamic therapy drugs by combining a zinc phthalocyanine sensitizer with TSPO or EGFR binding groups: the impact of the number of targeting agents on biological activity.

Drug-targeted delivery has become a top priority in the world of medicine in order to develop more efficient therapeutic agents. This is important as a critical underlying problem in cancer therapy stems from the inability to deliver active therapeutic substances directly to tumor cells without causing collateral damage. In this work, zinc(II) phthalocyanine (ZnPc) was selected as a sensitizer and was linked to different targeting agents, which would be recognized by overexpressed proteins in cancer cells. As targeting agents, we first selected the two ligands (DAA1106, PK11195) of the translocator protein (TSPO) and then Erlotinib a binding group of the ATP domain of tyrosine kinase in epidermal growth factor (EGFR). ZnPc was connected via an ethylene glycol chain to either one (n = 1) or four (n = 4) targeting agents. The biological activity of these conjugates ZnPc(ligand)n was investigated on MDA-MB-231 breast human cancer cells and human hepatoma HepG2 cells, first in the dark (cytotoxicity) and then under irradiation (photodynamic therapy). The dark cytotoxicity was extremely low (IC50 ≥ 50 µM) for all of these compounds, which is a required criterion for further photodynamic application. After irradiation at 650 nm, only the conjugates bearing one targeting ligand such as ZnPc-[DAA1106]1, ZnPc-[PK11195]1, and ZnPc-[Erlo]1 showed photodynamic activity, while those linked to 4 targeting agents were inactive. Importantly, fluorescence imaging microscopy showed the colocalization of ZnPc-[DAA1106]1, ZnPc-[PK11195]1 and ZnPc-[erlo]1, at mitochondria, a result that justifies the observed photodynamic activity of these conjugates. This study first shows the impact of the number and the mode of organization of targeting agents on the ability of the sensitizer to cross the cell membrane. When zinc(II) phthalocyanine carries a single targeting agent, a significant photodynamic activity on MDA-MB-231 breast human cancer cells was measured and localization at the mitochondria was demonstrated by fluorescence imaging, thus proving the potential of the sensitizer linked to a targeting agent to improve selectivity. Another important conclusion from this study for the design of future effective PDT drugs using multivalence effects is to control the arrangement of the targeting agents in order to design molecules that will be able to pass the cell membrane barriers.

Charge Recombination Deceleration by Lateral Transfer of Electrons in Dye-Sensitized NiO Photocathode.

Control of charge separation and recombination is critical for dye-sensitized solar cells and photoelectrochemical cells, and for p-type cells, the latter process limits their photovoltaic performance. We speculated that the lateral electron hopping between dyes on a p-type semiconductor surface can effectively separate electrons and holes in space and retard recombination. Thus, device designs where lateral electron hopping is promoted can lead to enhanced cell performance. Herein, we present an indirect proof by involving a second dye to monitor the effect of electron hopping after hole injection into the semiconductor. In mesoporous NiO films sensitized with peryleneimide (PMI) or naphthalene diimide (NDI) dyes, dye excitation led to ultrafast hole injection into NiO from either excited PMI* (τ < 200 fs) or NDI* (τ = 1.2 ps). In cosensitized films, surface electron transfer from PMI- to NDI was rapid (τ = 24 ps). Interestingly, the subsequent charge recombination (ps-µs) with NiO holes was much slower when NDI- was generated by electron transfer from PMI- than when NDI was excited directly. We therefore indicate that the charge recombination is slowed down after the charge hopping from the original PMI sites to the NDI sites. The experimental results supported our hypothesis and revealed important information on the charge carrier kinetics for the dye-sensitized NiO photoelectrode system.

New sulfonated perylene diimide pyrazolate ligands: a simple route toward n-type redox-active hybrid materials.

We report the synthesis and the in depth electrochemical study of two novel electron accepting sulfonated perylene diimide pyrazolate ligands. Bridging the sulfone moieties of the perylene core unexpectedly affected the optical and electronic properties as evidenced by spectroelectrochemical investigation. Notably, we achieved a significant lowering of the LUMO level to -4.83 eV, ranking the ligand among the best electron acceptors via a straightforward synthetic procedure. These ligands can be foreseen for the development of n-type functional materials.

Push-Pull Phenoxazine-Based Sensitizers for p-Type DSSCs: Effect of Acceptor Units on Photovoltaic Performance.

Finding new efficient p-type sensitizers for NiO photocathodes is a great challenge for the development of promising low-cost tandem dye-sensitized solar cells (DSSCs). Now, the focus of researchers investigating these cells has been to create high-performance p-type systems. With this intention, herein, the design and synthesis of six new phenoxazine-based donor-acceptor (D-A)-configured organic dyes PO1-6 was reported, comprising different acceptor moieties specially designed for the sensitization of mesoporous p-type semiconductor NiO for the construction of p-type DSSCs (p-DSSCs). This work includes structural, photophysical, thermal, electrochemical, theoretical, and photoelectrochemical studies of these dyes, including evaluation of their structure-property relationships. The optical studies revealed that PO1-6 displayed adequate absorption and emission features in the range of 480-550 and 560-650 nm, respectively, with a bandgap in the order of 2.05-2.40 eV, and their thermodynamic parameters favored an efficient interfacial charge transfer involving NiO. Among the six new dyes, the device based on sensitizer PO2 carrying electron-withdrawing 1,3-diethyl-2-thiobarbituric acid achieved the highest power conversion efficiency of 0.031 % (short-circuit current density=0.89 mA cm-2 , open-circuit voltage=101 mV, and fill factor=35 %). Conclusively, the study furnishes an understanding of the intricacies involved in the structural modification of phenoxazine-based sensitizers to further ameliorate the performance of the p-type DSSCs.

Transparent and Colorless Dye-Sensitized Solar Cells Based on Pyrrolopyrrole Cyanine Sensitizers.

The development of transparent solar cells extends the applications of photovoltaics by offering the opportunity to substitute the gigantic surface coverage of windows by solar panels to produce electricity. Herein, we report a new family of NIR-sensitizers based on pyrrolopyrrole cyanine dyes, particularly efficient for the development of fully transparent and colorless dye-sensitized solar cells since a record efficiency of 2.5 % was achieved with an average visible transmittance (AVT) of 76 % and a color rending index (CRI) of 93.

Photoinduced Delamination of Metal-Organic Framework Thin Films by Spatioselective Generation of Reactive Oxygen Species.

Metal-organic frameworks (MOFs) built from different building units offer functionalities going far beyond gas storage and separation. In connection with advanced applications, e.g., in optoelectronics, hierarchical MOF-on-MOF structures fabricated using sophisticated methodologies have recently become particularly attractive. Here, we demonstrate that the structural complexity of MOF-based architectures can be further increased by employing highly spatioselective photochemistry. Using a layer-by-layer, quasi-epitaxial synthesis method, we realized a photoactive MOF-on-MOF hetero-bilayer consisting of a porphyrinic bottom layer and a tetraphenylethylene (TPE)-based top layer. Illumination of the monolithic thin film with visible light in the presence of oxygen gas results in the generation of reactive oxygen species (1O2) in the porphyrinic bottom layer, which lead to a photocleavage of the TPE units at the internal interface. We demonstrate that this spatioselective photochemistry can be utilized to delaminate the top layers, yielding two-dimensional (2D) MOF sheets with well-defined thickness. Experiments using atomic force microscopy (AFM) demonstrate that these platelets can be transferred onto other substrates, thus opening up the possibility of fabricating planar MOF structures using photolithography.

Molecular Triad Containing a TEMPO Catalyst Grafted on Mesoporous Indium Tin Oxide as a Photoelectrocatalytic Anode for Visible Light-Driven Alcohol Oxidation.

Photoelectrochemical cells based on semiconductors are among the most studied methods of artificial photosynthesis. This study concerns the immobilization, on a mesoporous conducting indium tin oxide electrode (nano-ITO), of a molecular triad (NDADI-P-Ru-TEMPO) composed of a ruthenium tris-bipyridine complex (Ru) as photosensitizer, connected at one end to 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) as alcohol oxidation catalyst and at the other end to the electron acceptor naphthalenedicarboxyanhydride dicarboximide (NDADI). Light irradiation of NDADI-P-Ru-TEMPO grafted to nano-ITO in a pH 10 carbonate buffer effects selective oxidation of para-methoxybenzyl alcohol (MeO-BA) to para-methoxybenzaldehyde with a TON of approximately 150 after 1 h of photolysis at a bias of 0.4 V vs. SCE. The faradaic efficiency is found to be of 80±5 %. The photophysical study indicates that photoinduced electron transfer from the Ru complex to NDADI is a slow process and must compete with direct electron injection into ITO to have a better performing system. This work sheds light on some of the important ways to design more efficient molecular systems for the preparation of photoelectrocatalytic cells based on catalyst-dye-acceptor arrays immobilized on conducting electrodes.

Study of Cytotoxic and Photodynamic Activities of Dyads Composed of a Zinc Phthalocyanine Appended to an Organotin.

The combination of photodynamic therapy and chemotherapy is a promising strategy to enhance cancer therapeutic efficacy and reduce drug resistance. In this study two zinc(II) phthalocyanine-tin(IV) conjugates linked by a triethylene glycol chain were synthesized and characterized. In these complexes, the zinc(II) phthalocyanine was used as a potential photosensitizer for PDT and the tin complex was selected as cytostatic moiety. The two dyads composed of zinc(II) phthalocyanine and tin complexes exhibited high cytotoxicity, in absence of light stimulation, against MCF-7 human breast cancer cells with low LC50 values in the range of 0.016-0.453 µM. In addition, these complexes showed superior cytotoxicity than their mixture of equimolar component, accompanied with a higher activity towards cancer cells compared to human healthy fibroblasts. However, under irradiation of the zinc phthalocyanine unit (at 650 nm) no photodynamic activity could be detected, due to the most likely quenching of zinc(II) phthalocyanine singlet excited state by the nearby tin complex according to a photoinduced electron transfer process. This study demonstrates the potential of heterometallic anticancer chemotherapeutics composed of a zinc phthalocyanine and tin complex, and it highlights that the development of such conjugates requires that the sensitizer preserves its photophysical properties and in particular its singlet oxygen sensitization ability in the conjugate in order to combine the PDT activity with the cytotoxicity of the anticancer drug.

Synergetic anticancer activity of gold porphyrin appended to phenyl tin malonate organometallic complexes.

The discovery of novel anticancer chemotherapeutics is fundamental to treat cancer more efficiently. Towards this goal, two dyads consisting of a gold porphyrin appended to organotin(iv) entities were synthesized and their physicochemical and biological properties were characterized. One dyad contains a gold porphyrin connected to a tin(iv) cation via a malonate and two phenyl ligands (AuP-SnPh2), while the other contains two tin(iv) cations each chelated to one carboxylic acid group of the malonate and three phenyl ligands (AuP-Sn2Ph6). The mode of chelation of Sn(iv) to the malonate was elucidated by IR spectroscopy and 119Sn NMR. In the solid state, the complexes exist as coordination polymers in which the tin is penta-coordinated and bridged to two different malonate units. In solution the chemical shifts of 119Sn signals indicate that the tin complexes are in the form of monomeric species associated with a tetra-coordinated tin cation. The therapeutic potential of these new compounds was assessed by determining their cytotoxic activities on human breast cancer cells (MCF-7) and on healthy human fibroblasts (FS 20-68). The study reveals that the dyads are more potent anticancer drugs than the mixture of their individual components (gold porphyrin and reference tin complexes). Therefore, the covalent link of organotin complexes to a gold porphyrin induces a synergistic cytotoxic effect. The dyad AuP-SnPh2 shows high cytotoxicity (0.13 µM) against MCF-7 along with good selectivity for cancer cells versus healthy cells. Finally, it was also shown that the dyad AuP-Sn2Ph6 exhibits a very high anticancer activity (LC50 = 0.024 µM), but the presence of two tin units induces strong cytotoxicity on healthy cells too (LC50 = 0.032 µM). This study underscores, thus, the potential of the association of gold porphyrin and organotin complexes to develop anticancer metallo-drugs.

Tuning Optical Properties by Controlled Aggregation: Electroluminescence Assisted by Thermally-Activated Delayed Fluorescence from Thin Films of Crystalline Chromophores.

Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally-activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal-organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA-TPE (diphenylamine-tetraphenylethylene) chromophore, which is non-emissive in its solvated state due to vibrational quenching. Turning this DPA-TPE into a ditopic linker makes it possible to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, this work reports that the layer-by-layer process used for MOF thin film deposition allows the integration of the TADF-DPA-TPE in a functioning LED device.

Photocathode functionalized with a molecular cobalt catalyst for selective carbon dioxide reduction in water.

Artificial photosynthesis is a vibrant field of research aiming at converting abundant, low energy molecules such as water, nitrogen or carbon dioxide into fuels or useful chemicals by means of solar energy input. Photo-electrochemical reduction of carbon dioxide is an appealing strategy, aiming at reducing the greenhouse gas into valuable products such as carbon monoxide at low or without bias voltage. Yet, in such configuration, there is no catalytic system able to produce carbon monoxide selectively in aqueous media with high activity, and using earth-abundant molecular catalyst. Upon associating a p-type Cu(In,Ga)Se2 semi-conductor with cobalt quaterpyridine complex, we herein report a photocathode complying with the aforementioned requirements. Pure carbon dioxide dissolved in aqueous solution (pH 6.8) is converted to carbon monoxide under visible light illumination with partial current density above 3 mA cm-2 and 97% selectivity, showing good stability over time.

A Comparative Investigation of the Role of the Anchoring Group on Perylene Monoimide Dyes in NiO-Based Dye-Sensitized Solar Cells.

The anchoring group of a sensitizer may strongly affect the overall properties and stability of the resulting dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthetic solar cells (DSPECs). The properties of seven perylene monoimide (PMI) dyes have been comprehensively studied for their immobilization on nanocrystalline NiO film. The PMI dyes differ only by the nature of the anchoring group, which are: carboxylic acid (PMI-CO2 H), phosphonic acid (PMI-PO3 H2 ), acetyl acetone (PMI-acac), pyridine (PMI-Py), aniline (PMI-NH2 ), hydroxyquinoline (PMI-HQ), and dipicolinic acid (PMI-DPA). The dyes are investigated by cyclic voltammetry and spectroelectrochemistry and modeled by TD-DFT quantum chemical calculations. The mode of binding of these anchoring groups is investigated by infrared spectroscopy and the stability of the binding to NiO surface is studied by desorption experiments in acidic and basic media. The phosphonic acid group is found to offer the strongest binding to the NiO surface in terms of stability and dye loading. Finally, a photophysical study by ultrafast transient absorption spectroscopy shows that all dyes inject a hole in NiO with rate constants on a subpicosecond timescale and display similar charge recombination kinetics. The photovoltaic properties of the dyes show that PMI-HQ and PMI-acac give the highest photovoltaic performances, owing to a lower degree of aggregation on the surface.

Synthesis and Anticancer Activity of Gold Porphyrin Linked to Malonate Diamine Platinum Complexes.

Recently, gold(III) porphyrins have gained great interest as anticancer drugs not only for the stability of gold(III) but also for the functionalization of the porphyrin to allow bridging with another metal such as platinum(II). We report here, for the first time, the synthesis of three new bimetal compounds containing a gold(III) porphyrin conjugated to a platinum diamine moiety through malonate bridging to obtain enhanced cytotoxicity from both metals combined with the phototoxicity of the porphyrin. The three complexes differ in the type of diamine ligand around platinum(II): ammonia (NH3), cyclohexanediamine (CyDA), and pyridylmethylamine (Py). The synthesis was carried out using the complexation of activated malonic acid derivatives with aquadiaminoplatinum(II) complexes, and the products were characterized by IR, NMR, mass spectra, and elementary analysis. The cytotoxic activity of the conjugates was screened in both healthy cell lines and cancer cell lines, human fibroblast cells (FS-68) and human breast cancer cells (MCF-7), and was compared to that of the corresponding platinum(II) complexes. The cyclohexyldiamine (CyDA) derivative exhibited the greatest cytotoxic effect among the series. The results showed that Au(III)/Pt(II) conjugates are more potent by 2-5.6-fold than the corresponding platinum complexes. Moreover, the dyad AuP-PtCyDA is 18% more potent and also more selective toward cancer cells than the parent gold porphyrin substituted with malonic acid. On the other hand, the IC50 of the dyad AuP-PtCyDA is 43% lower than that of AuTPP but is more selective toward healthy cells. Singlet oxygen measurements indicated that gold(III) porphyrin derivatives are poor oxygen sensitizers and cell death occurred potentially due to generation of other reactive oxygen species (ROS) upon reductive quenching of the gold porphyrin excited state. In addition, the increase in cancer cell death obtained after light irradiation is totally absent in healthy cells, demonstrating the specificity of this PDT treatment on cancer cells. Our findings imply that the incorporation of two different cytotoxic metals in the same molecule represents a remarkable cytotoxic effect in comparison to traditional homometallic Pt(II) drugs.

A de novo strategy for predictive crystal engineering to tune excitonic coupling.

In molecular solids, the intense photoluminescence (PL) observed for solvated dye molecules is often suppressed by nonradiative decay processes introduced by excitonic coupling to adjacent chromophores. We have developed a strategy to avoid this undesirable PL quenching by optimizing the chromophore packing. We integrated the photoactive compounds into metal-organic frameworks (MOFs) and tuned the molecular alignment by introducing adjustable "steric control units" (SCUs). We determined the optimal alignment of core-substituted naphthalenediimides (cNDIs) to yield highly emissive J-aggregates by a computational analysis. Then, we created a large library of handle-equipped MOF chromophoric linkers and computationally screened for the best SCUs. A thorough photophysical characterization confirmed the formation of J-aggregates with bright green emission, with unprecedented photoluminescent quantum yields for crystalline NDI-based materials. This data demonstrates the viability of MOF-based crystal engineering approaches that can be universally applied to tailor the photophysical properties of organic semiconductor materials.

Solar electricity and fuel production with perylene monoimide dye-sensitised TiO2 in water.

Dye-sensitisation of TiO2 and other metal oxides is an established strategy to couple solar light harvesting with efficient charge separation for the production of electricity in dye-sensitised solar cells (DSCs) or fuels in dye-sensitised semiconductor photocatalysis (DSP). Perylene monoimide (PMI) dyes have emerged as promising organic dyes, but they have not previously been used in a functional assembly with TiO2 in aqueous solution. Here, five novel PMI dyes bearing carboxylic acid, phosphonic acid, acetylacetone, hydroxyquinoline or dipicolinic acid anchoring groups for attachment onto TiO2 are reported. We identified functional DSC and DSP systems with PMI-sensitised TiO2 in aqueous solution, which permitted a side-by-side comparison with respect to performance between the two systems. Structure-activity relationships allowed us to suggest anchor-condition-system associations to suit specific anchoring groups at various pH values, and with different electron mediators (redox couple or sacrificial electron donor) and catalysts in DSC and DSP schemes. A DSC sensitised with the hydroxyquinoline-modified PMI dye reached the highest short-circuit current density (J SC ≈ 1.4 mA cm-2) in aqueous electrolyte solution during irradiation with simulated solar light. This dye also achieved a turnover number (TONPMI) of approximately 4900 for sacrificial proton reduction after 24 h irradiation in a DSP scheme with Pt as a H2-evolving co-catalyst at pH 4.5. This performance was only surpassed by the carboxylic acid-bearing dye, which reached a new benchmark turnover number (TONPMI ≈ 1.1 × 104 after 72 h) for an organic dye in nanoparticulate DSP for solar fuel production. At higher pH (8.5), our results showed that the phosphonic acid group allows for higher performance due to a stronger anchoring ability. This study provides a platform for aqueous PMI dye-sensitised TiO2 chemistry and gives valuable insights into the performance of different anchoring groups in DSC and DSP systems.