Borylated Subphthalocyanines: Versatile Precursors for the Preparation of Functional Bowl-Shaped Aromatics

The peripheral borylation of porphyrinoids has become a key step to prepare advanced functional materials. This study reports the synthesis, electronic properties, and reactivity of borylated subphthalocyanines. These compounds, which are prepared by Suzuki–Miyaura borylation in excellent yields, are easily purified, display a great stability, and serve as powerful starting materials for the post-functionalization of SubPcs via cross-coupling reactions. Remarkably, this novel approach is more efficient than the methodologies already described and enables the preparation of exotic systems, such as SubPc dimeric species linked by C−C bonds, which are not accessible so far and present promising properties for optoelectronic devicesWe gratefully acknowledge financial support from MICINN (PID2020-116490GB-I00 and TED2021-131255B-C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“MATERIALES DISRUPTIVOS BIDIMENSIONALES (2D)” (MAD2D-CM)-MRR MATERIALES AVANZADOS], and the European Union through the Next Generation EU funds). IMDEA Nanociencia acknowledges support from the Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. Fellowshi

Acceleration of the Diels-Alder Reaction between 9-functionalized anthracenes and C60/C70 in the cavity of a water soluble subphthalocyanine cage

Herein we report on the acceleration of the Diels-Alder reaction between a series of 9-functionalized anthracenes and C60/C70 encapsulated in a water-soluble metallo-organic Pd(II)-subphthalocyanine cage (SubPc-cage), which performs as a catalytic molecular reactor that provides a beneficial hydrophobic environment. Negatively and positively charged anthracenes do not react either with C60 or C70, due to a favored solvation in water medium and/or to detrimental interactions with positively-charged Pd(II) corners of SubPc-cage. Experiments with C60 and C70 rendered parallel results, although C70 proved more reactive, leading to anthracene cycloadducts by reaction in the α bonds. All the results have been rationalized by theoretical calculations at the GFN2-xTB levelPID2020-116490GB-I00, PID2020-115801RB-C21, TED2021-131255B-C43, MAD2D-C

Subphthalocyaninato boron(III) hydride: synthesis, structure and reactivity

Subphthalocyanine (SubPc) chemistry has been limited so far by their high sensitivity toward strong nucleophiles. In particular, the substitution of the axial chlorine atom by a nucleophilic group in the case of less-reactive SubPcs, such as those bearing electron-withdrawing peripheral substituents, presents some limitations and requires harsh conditions. By taking advantage of the electrophilic character of DIBAL-H, it has been possible to prepare for the first time SubPc-hydride derivatives that exhibit high reactivity as hydroboration reagents of aldehydes. This hydride transfer requires using a typical carbonyl activator (trimethylsilyl triflate) and only one equivalent of aldehyde, affording SubPcs with an axial benzyloxy group in good yield. This transformation has proven to be a useful alternative method for the axial functionalisation of dodecafluoroSubPc, a paradigmatic SubPc derivative, by using electrophiles for the first time. Considering the increasing interest in SubPcs as electron-acceptor semiconductors with remarkable absorption in the visible range to replace fullerene in organic photovoltaic (OPV) devices, it is of the utmost importance to develop new synthetic methodologies for their axial functionalisationFinancial support from Spanish MINECO and MICINN (CTQ2017- 85393-P, PGC2018-094644-B-C21, PDI2019-110091GB-I00) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, grant SEV2016-0686). J.L. and L.T. acknowledge MECD, Spain, for a F.P.U. fellowship. I.C. and L.M

Anthracene-Fused Oligo-BODIPYs: a new class of π-extended NIR-absorbing materials

Large π-conjugated systems are key in the area of molecular materials. Herein, we prepare via AuI - catalyzed cyclization a series of fully π-conjugated anthracene-fused oligo-BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by means of Density Functional Theory (DFT) calculations. Depending on the size and shape of the π-conjugated skeleton, unique features—such as face-to-face supramolecular organization, NIR absorption and fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features render them valuable for technological applicationsments We gratefully acknowledge financial support from the Spanish MICINN through Projects PID2020-116490GB-I00 (Porphyrinoids) and TED2021-131255B-C43 (PERSOLAR). We also thank financial support to the Comunidad de Madrid (MAD2D-CM) and MICINN through project “Materiales disruptivos bidimensionales (2D)” within the Plan de recuperación, transformación y resiliencia (Materiales avanzados). IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. fellowship. European Commission under the Marie Sklodowska-Curie Action Cofund 2015 (EU project 713366-InterTalentum) is acknowledged for the support for G.D.S. Generous allocation of computational time from the Centro de Computación Científica UAM is gratefully acknowledged. Work in Erlangen was supported by the Deutsche Forschungsgemeinschaft (DFG) through SFB 953 project B10 and the Bavarian Collaborative Research Project “Solar Technologies go Hybrid” (SolTech

Modulating the electron transporting properties of Subphthalocyanines for inverted perovskite solar cells

The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of p-i-n PSCs. Specifically, ETMs based on three SubPcs (with either six or twelve peripheral fluorine and chlorine atoms) have been incorporated into PSCs with the perovskite layer deposited by solution processing (CsFAMAPbIBr). The device performance and morphology of these devices are deeply analyzed using several techniques, and the interfacial effects induced by the SubPcs are studied using photoluminescence and TR-PL. It is observed that the device stability is significantly improved upon insertion the SubPc layer. Moreover, the impact of the SubPc layer-thickness is assessed. Thus, a maximum power conversion efficiency of 13.6% was achieved with the champion devic

Surveillance of Viruses in Wild Fish Populations in Areas around the Gulf of Cadiz (South Atlantic Iberian Peninsula)

This report describes a viral epidemiological study of wild fish around the Gulf of Cadiz (southwestern Iberian Peninsula) and is focused on infectious pancreatic necrosis virus (IPNV), viral hemorrhagic septicemia virus (VHSV), and viral nervous necrosis virus (VNNV). One fish species (Chelon labrosus) was sampled inside the gulf, at the mouth of the San Pedro River. Another 29 were sampled, in three oceanographic campaigns, at sites around the Bay of Cadiz. The fish were processed individually and subjected to isolation in cell culture and molecular diagnosis. VHSV was not isolated from any species. Thirteen IPNV-type isolates were obtained from barracuda (Sphyraena sphyraena), axillary seabream (Pagellus acarne), common two-banded seabream (Diplodus vulgaris), common pandora (P. erythrinus), Senegal seabream (D. bellottii), and surmullet (Mullus surmuletus). Six VNNV isolates were obtained from axillary seabream, common pandora, black seabream (Spondyliosoma cantharus), red mullet (Mullet barbatus), Lusitanian toadfish (Halobatrachus didactylus), and tub gurnard (Chelidonichtys lucerna). In the river mouth, viruses were detected only after reamplification, obtaining prevalence percentages of IPNV and VNNV (44.4 and 63.0%, respectively) much higher than those observed in the oceanographic campaigns (25.7 and 19.6%, respectively). The opposite results were obtained in the case of VHSV after reamplification: 11.1% in the river mouth and 43.6% in the oceanic locations. Analyzing the results with respect to the proximity of the sampling sites to the coast, an anthropogenic influence on wild fish is suggested and discussed. The type of viruses and the presence of natural reassortants are also discussed

Supramolecular subphthalocyanine cage as catalytic container for the functionalization of fullerenes in water

Herein we report the first example of a supramolecular cage that works as a catalytic molecular reactor to perform transformations over fullerenes in aqueous medium. Taking advantage of the ability of metallo–organic Pd(II)-subphthalocyanine (SubPc) capsules to form stable host:guest complexes with C60, we have prepared a water-soluble cage that provides a hydrophobic environment for conducting cycloadditions over encapsulated C60, namely, Diels–Alder reactions with anthracene. Indeed, the presence of catalytic amounts of SubPc cage dissolved in water promotes coencapsulation of insoluble C60 and anthracene substrates, allowing the reaction to occur inside the cavity under mild conditions. The lower stability of the host: guest complex with the resulting C60 cycloadduct facilitates its displacement by pristine C60, which grants catalytic turnover. Moreover, bis-addition compounds are regioselectively formed inside the cage when using excess anthracenements Financial support from the Spanish MCIN/AEI/10.13039/ 501100011033 (PID2020-116490GB-I00, PID2020- 115801RB-C21, TED2021-131255B-C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados], and the European Union through the Next Generation EU funds is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). S.K. acknowledges MSCA grant (101028059), and J.L. acknowledges MECD, Spain, for a F.P.U. fellowshi

Controlling Electronic Events Through Rational Structural Design in Subphthalocyanine–Corrole Dyads: Synthesis, Characterization, and Photophysical Properties

Porphyrinoids are considered perfect candidates for their incorporation into electron donor–acceptor (D–A) arrays due to their remarkable optoelectronic properties and low reorganization energies. For the first time, a series of subphthalocyanine (SubPc) and corrole (Cor) were covalently connected through a short-range linkage. SubPc axial substitution strategies were employed, which allowed the synthesis of the target molecules in decent yields. In this context, a qualitative synthetic approach was performed to reverse the expected direction of the different electronic events. Consequently, in-depth absorption, fluorescence, and electrochemical assays enabled the study of electronic and photophysical properties. Charge separation was observed in cases of electron-donating Cors, whereas a quantitative energy transfer from the Cor to the SubPc was detected in the case of electron accepting CorsThis work was supported by the Spanish MINECO, PID2020- 116490GB I00 (Porphyrinoids, T.T) and by the Italian PRIN MIUR “SUNSET“ 2017EKCS35_002. IMDEA-Nanociencia also acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686

A novel electron Donor-Acceptor Carbazole-Zn(II)Phthalocyanine – Perfluorinated Subphthalocyanine Conjugate: synthesis, characterization, and photoinduced electron-transfer

Porphyrinoids are considered perfect candidates for the preparation of model electron donor-acceptor (D-A) systems as they enable fast and efficient photoinduced electron transfer. Herein, we report on the synthesis and photophysical characterization of a ZnPc SubPc conjugate covalently connected through a short-range alkyne spacer. We designed and prepared the conjugate, which comprise, on the one hand, a perfluorinated SubPc with strong electron acceptor character and, on the other, a Pc peripherally functionalized with carbazoles with strong electron donor character. Photoinduced electron transfer events are in-depth analyzed by several techniques, including steady-state absorption, time-resolved emission and transient absorption measurements on different time scales. Our studies confirm a full charge separation occurring from a photoexcited charge transfer state68. Acknowledgements Financial support from Spanish MINECO (PID2020-116490GB I00, Porphyrinoids) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. fellowship. Kuwait Foundation for the Advancement of Science (KFAS) and the RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS 03/01, GS 01/03, GS 01/05) is acknowledged. Work in Erlangen was supported by the Deutsche Forschungsgemeinschaft (DFG) through SFB 953 project B10 and the Bavarian Collaborative Research Project “Solar Technologies go Hybrid" (SolTech