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

Influence of substituents of Perylenebisimides on the surface energy and wettability: A systematic structure–property relationship analysis

This paper seeks to elucidate the influence on the surface wettability of a variety of substituents located in different positions of the perylene bisimide (PBI) core (ortho versus imide) with distinct electron-donor or -withdrawing character and diverse steric demand, using for this more than 20 planar PBIs. The correlation between the polarity of the individual functional group on the PBI and the surface wettability has been addressed by means of substituent descriptors in terms of Hansch-Fujita π parameter, Hammett σmeta and σpara constants, and steric parameters (Taft-Dubois Es’ and Charton υ). With these parameters, a quantitative structure–property relationship (QSPR) analysis has been performed using multivariable linear regression (MLR) fittings. The relationship of Surface Energy, determined by the static contact angle method with three different solvents, to structural properties of PBIs is described. As well, the polar and dispersive contributions have been determined. For planar PBIs, a predominant influence of the substituents in the imide position on the surface wettability has been found despite of the electronic nature and steric hindrance of the substituents simultaneously located in ortho positions. This effect is more pronounced with the longer alkyl substituents at the imide position. This study paves the way for a rational chromophore design considering the on surface behavior, which will ultimately condition the contact and thus their performance in optoelectronic devices

Electrochemical sensors modified with combinations of sulfur containing phthalocyanines and capped gold nanoparticles: A study of the influence of the nature of the interaction between sensing materials

Producción CientíficaVoltametric sensors formed by the combination of a sulfur-substituted zinc phthalocyanine (ZnPcRS) and gold nanoparticles capped with tetraoctylammonium bromide (AuNPtOcBr) have been developed. The influence of the nature of the interaction between both components in the response towards catechol has been evaluated. Electrodes modified with a mixture of nanoparticles and phthalocyanine (AuNPtOcBr/ZnPcRS) show an increase in the intensity of the peak associated with the reduction of catechol. Electrodes modified with a covalent adduct-both component are linked through a thioether bond-(AuNPtOcBr-S-ZnPcR), show an increase in the intensity of the oxidation peak. Voltammograms registered at increasing scan rates show that charge transfer coefficients are different in both types of electrodes confirming that the kinetics of the electrochemical reaction is influenced by the nature of the interaction between both electrocatalytic materials. The limits of detection attained are 0.9 × 10−6 mol∙L−1 for the electrode modified with the mixture AuNPtOcBr/ZnPcRS and 1.3 × 10−7 mol∙L−1 for the electrode modified with the covalent adduct AuNPtOcBr-S-ZnPcR. These results indicate that the establishment of covalent bonds between nanoparticles and phthalocyanines can be a good strategy to obtain sensors with enhanced performance, improving the charge transfer rate and the detection limits of voltammetric sensors.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (projects RTI2018-097990-B-I00 / CTQ2017-87102-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA275P18

Efficient passivated phthalocyanine-quantum dot solar cells

The power conversion efficiency of CdSe and CdS quantum dot sensitized solar cells is enhanced by passivation with asymmetrically substituted phthalocyanines. The introduction of the phthalocyanine dye increases the efficiency up to 45% for CdSe and 104% for CdS. The main mechanism causing this improvement is the quantum dot passivation. This study highlights the possibilities of a new generation of dyes designed to be directly linked to QDs instead of the TiO2 electrodes.This work has been supported by the Spanish Ministry of Science and Innovation, Generalitat Valenciana and the European FEDER funds (CTQ2011-26455, PROMETEO 2012/010, ACOMP/2013/024 and ISIC/2012/008)

Diels–Alder reaction on perylenediimides: synthesis and theoretical study of core-expanded diimides

A one-step reaction for the fusion of aromatic rings to one or both bay areas of perylenediimides using benzynes is presented. Yields as high as 70% for naphthoperylenendiimide 2 and 80% for dibenzocoronenediimide 3 are obtained. The reaction is also carried out using substituted benzynes, heteroaromatic benzynes and substituted perylenediimides. A combined experimental/theoretical approach, based on measuring redox and absorption/emission properties and performing density functional theory calculations, indicates that increasing the π-skeleton of PDIs transversally leads to significant and unexpected changes in the electronic, redox and optical properties. The observed trends are rationalized in terms of molecular orbital topology and overlap according to three different levels of core expansion, and can be used as design principles for obtaining PDIs with improved functionalities

Improving the performance of electrochemical sensors by means of synergy. Combinations of gold nanoparticles and phthalocyanines

Producción CientíficaVoltammetric sensors chemically modified with combinations of two electrocatalytic materials: tetraoctylammonium bromide capped gold nanoparticles (AuNPNBr) and a sulphur containing zinc phthalocyanine derivative (ZnPcRS) are reported. The electrocatalytic effects in the detection of catechol have been analyzed in sensors obtained by direct mixing (AuNPNBr/ZnPcRS) and in sensors modified with an adduct where both components are linked covalently (AuNPNBr-S-ZnPcR). Results demonstrate that the nature of the interaction between both components modifies the electrocatalytic properties. The AuNPNBr/ZnPcRS mixture improves the electron transfer rate of the catechol reduction, with limits of detection of 10−6 M. The covalent adduct AuNPNBr-S-ZnPcR enhances the response rate of the oxidation of the catechol with limits of detection of 10−7 M.Ministerio de Economía y Empresa-FEDER (AGL2015-67482-R)Junta de Castilla y Leon - FEDER (VA-032U13)Junta de Castilla y Leon, (grant BOCYL-D-4112015-9

Large-Size Star-Shaped Conjugated (Fused) Triphthalocyaninehexaazatriphenylene

Star-shaped triphthalocyaninehexaazatriphenylene 1 was synthesized via condensation between a new building block 1,2-diaminophthalocyanine and cyclohexanehexaone. Compound 1 represents the largest star-shaped phthalocyanine-fused hexaazatriphenylene reported so far. This largely expanded phthalocyanine shows good solubility and has a strong tendency to aggregate in both solution and on surface, indicating its potential as active component in organic electronic devices.This research was financially supported by the Spanish Ministry of Economy and Competitiveness (Mineco) of Spain [CTQ2014-55798-R, CTQ2015-71936-REDT, CTQ2013-40480-R and “Severo Ochoa” Programme for Centres of Excellence in R&D (SEV-2015-0496)], Generalitat Valenciana (Prometeo 2012/010), the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN) and by ERC StG 2012-306826 e-GAMES. A. C. acknowledges the Materials Science PhD program of UAB.Peer reviewe

Correction: Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities

Correction for ‘Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities’ by Ritesh Haldar et al., Chem. Sci., 2020, DOI: 10.1039/d0sc02436

1,7-Bay-Substituted Perylenediimide Derivative with Outstanding Laser Performance

Efficient ASE at wavelengths >620 nm from PS films doped with a bay-substituted perylenediimide (PDI) derivative is reported. The maximum PDI content is around 40 times larger than in prior studies. The ability to introduce large dye amounts into the film without photoluminescence (PL) quenching allows very high PL and ASE efficiencies with low thresholds. A distributed feedback (DFB) laser device using one of the best-performing films is fabricated and characterized.We thank support from the Spanish Government (MINECO), the European Community (FEDER) and the Generalitat Valenciana through MAT-2011–28167-C02, CTQ2011–26455, PROMETEO 2012/010 and ISIC/2012/008, as well as to the University of Alicante and the University Miguel Hernández de Elche

Diphenylphenoxy-Thiophene-PDI Dimers as Acceptors for OPV Applications with Open Circuit Voltage Approaching 1 Volt

Two new perylenediimides (PDIs) have been developed for use as electron acceptors in solution-processed bulk heterojunction solar cells. The compounds were designed to exhibit maximal solubility in organic solvents, and reduced aggregation in the solid state. In order to achieve this, diphenylphenoxy groups were used to functionalize a monomeric PDI core, and two PDI dimers were bridged with either one or two thiophene units. In photovoltaic devices prepared using PDI dimers and a monomer in conjunction with PTB7, it was found that the formation of crystalline domains in either the acceptor or donor was completely suppressed. Atomic force microscopy, X-ray diffraction, charge carrier mobility measurements and recombination kinetics studies all suggest that the lack of crystallinity in the active layer induces a significant drop in electron mobility. Significant surface recombination losses associated with a lack of segregation in the material were also identified as a significant loss mechanism. Finally, the monomeric PDI was found to have sub-optimum LUMO energy matching the cathode contact, thus limiting charge carrier extraction. Despite these setbacks, all PDIs produced high open circuit voltages, reaching almost 1 V in one particular caseThis work was supported by the Spanish Ministry of Economy, Industry and Competitiveness (MEIC) (TEC2015-71324-R, CTQ2014-55798-R and TEC2015-71915-REDT (MINECO/FEDER))This work was supported by the Catalan Institution for Research and Advanced Studies (ICREA) (ICREA “Academia Award”, AGAUR 2017 SGR 017SGR1527