Synthesis of a New Co Metal–Organic Framework Assembled from 5,10,15,20-Tetrakis((pyridin-4-yl) phenyl)porphyrin “Co-MTPhPyP” and Its Application to the Removal of Heavy Metal Ions

The synthesis of a Co metal–organic framework assembled from 5,10,15,20-tetrakis((pyridin-4-yl)phenyl)porphyrin; TPhPyP) “Co-MTPhPyP” is reported. The TPhPyP ligand was synthesized via aldehyde condensation in 28% yield and characterized by 1H nuclear magnetic resonance (1H NMR), Fourier-transform infrared (FTIR), high-resolution mass spectrometry (HRMS), and UV-visible spectroscopy (UV-vis). Co-MTPhPyP was prepared by the solvothermal method from TPhPyP and CoCl2·H2O in 55% yield and characterized by X-ray powder diffraction (XRD), FTIR, thermogravimetric analysis (TGA), field-emission scanning electron microscopy with energy-dispersive X-ray (FESEM-EDS), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS), showing a particle size distribution of 418 ± 58 nm. The sorption properties of the Co-MTPhPyP for the effective removal of Pb(II) and Cu(II) were evaluated in an aqueous medium and Cthe results showed uptake capacities of 383.4 and 168 mg of the metal g−1 after 2 h, respectively. Kinetic studies of Pb(II) adsorption by Co-MTPhPyP were adjusted to the pseudo-second-order model with a maximum adsorption capacity of 458.8 mg g−1 at 30 min of exposition

High-boron-content porphyrin-cored aryl ether dendrimers: controlled synthesis, characterization, and photophysical properties

The synthesis and characterization of a set of poly(aryl ether) dendrimers with tetraphenylporphyrin as the core and 4, 8, 16, or 32 closo-carborane clusters are described. A regioselective hydrosilylation reaction on the allyl-terminated functions with carboranylsilanes in the presence of Karstedt's catalyst leads to different generations of boron-enriched dendrimers. This versatile approach allows the incorporation of a large number of boron atoms in the dendrimers' periphery. Translational diffusion coefficients (D) determined by DOSY NMR experiments permit estimation of the hydrodynamic radius (RH) and molecular size for each dendrimer. Furthermore, a notable correlation between D and the molecular weight (MW) is found and can be used to predict their overall size and folding properties. The UV-vis and emission behavior are not largely affected by the functionalization, therefore implying that the presence of carboranes does not alter their photoluminescence properties.This work has been supported by the Junta de Andalucı́a, programa Proyectos de Excelencia (P11-FQM-8229) and Ministerio de Economı́a y Competitividad (CTQ2013-44670-R and CTQ2012-32436). J.C.-G. thanks the CSIC for an Intramural grant. E.X.-F. thanks CONACYT for a Ph.D. fellowship (211329) and Programa de Cooperación Cientı́fica UNAM-CSIC and CONACYT for financial support.Peer reviewe

High-Boron-Content Porphyrin-Cored Aryl Ether Dendrimers: Controlled Synthesis, Characterization, and Photophysical Properties

The synthesis and characterization of a set of poly(aryl ether) dendrimers with tetraphenylporphyrin as the core and 4, 8, 16, or 32 closo-carborane clusters are described. A regioselective hydrosilylation reaction on the allyl-terminated functions with carboranylsilanes in the presence of Karstedt's catalyst leads to different generations of boron-enriched dendrimers. This versatile approach allows the incorporation of a large number of boron atoms in the dendrimers' periphery. Translational diffusion coefficients (D) determined by DOSY NMR experiments permit estimation of the hydrodynamic radius (RH) and molecular size for each dendrimer. Furthermore, a notable correlation between D and the molecular weight (MW) is found and can be used to predict their overall size and folding properties. The UV vis and emission behavior are not largely affected by the functionalization, therefore implying that the presence of carboranes does not alter their photoluminescence properties.Depto. de Química OrgánicaFac. de Ciencias QuímicasTRUEpu

Fluorescent BODIPY-Anionic Boron Cluster Conjugates as Potential Agents for Cell Tracking

A series of novel fluorescent BODIPY-anionic boron cluster conjugates bearing [B12H12]2- (5, 6), [3,3'-Co(1,2-C2B9H11)2]- (7, 8), and [3,3'-Fe(1,2-C2B9H11)2]- (9) anions have been readily synthesized from meso-(4-hydroxyphenyl)-4,4-difluoro-4-bora-3 a,4 a-diaza- s-indacene (BODIPY 4), and their structure and photoluminescence properties have been assessed. Linking anionic boron clusters to the BODIPY (4) does not alter significantly the luminescent properties of the final fluorophores, showing all of them similar emission fluorescent quantum yields (3-6%). Moreover, the cytotoxicity and cellular uptake of compounds 5-9 have been analyzed in vitro at different concentrations of B (5, 50, and 100 μg B/mL) using HeLa cells. At the lowest concentration, none of the compounds shows cytotoxicity and they are successfully internalized by the cells, especially compounds 7 and 8, which exhibit a strong cytoplasmic stain indicating an excellent internalization efficiency. To the best of our knowledge, these are the first BODIPY-anionic boron cluster conjugates developed as fluorescent dyes aiming at prospective biomedical applications. Furthermore, the cellular permeability of the starting BODIPY (4) was improved after the functionalization with boron clusters. The exceptional cellular uptake and intracellular boron release, together with the fluorescent and biocompatibility properties, make compounds 7 and 8 good candidates for in vitro cell tracking.The work was supported by Spanish Ministerio de Economía y Competitividad, MINECO, (CTQ2016-75150-R, MAT2017-86357-C3-3-R and “Severo Ochoa” Program for Centers of Excellence in R&D (SEV-2015-0496)) and Generalitat de Catalunya (2017-SGR-1720, 2017-SGR-503). J. C.-G. thanks CSIC for an Intramural Grant, J. C.-G. was enrolled in PhD Program of the UAB. The authors wish to thank the SCAC for flow cytometry assistance and the Servei de Microscopia at the UAB.Peer reviewe

High-Boron-Content Porphyrin-Cored Aryl Ether Dendrimers: Controlled Synthesis, Characterization, and Photophysical Properties

The synthesis and characterization of a set of poly­(aryl ether) dendrimers with tetraphenylporphyrin as the core and 4, 8, 16, or 32 <i>closo</i>-carborane clusters are described. A regioselective hydrosilylation reaction on the allyl-terminated functions with carboranylsilanes in the presence of Karstedt’s catalyst leads to different generations of boron-enriched dendrimers. This versatile approach allows the incorporation of a large number of boron atoms in the dendrimers’ periphery. Translational diffusion coefficients (<i>D</i>) determined by DOSY NMR experiments permit estimation of the hydrodynamic radius (<i>R</i>_H) and molecular size for each dendrimer. Furthermore, a notable correlation between <i>D</i> and the molecular weight (MW) is found and can be used to predict their overall size and folding properties. The UV–vis and emission behavior are not largely affected by the functionalization, therefore implying that the presence of carboranes does not alter their photoluminescence properties

Fluorescent BODIPY-Anionic Boron Cluster Conjugates as Potential Agents for Cell Tracking

A series of novel fluorescent BODIPY-anionic boron cluster conjugates bearing [B₁₂H₁₂]^2– (<b>5</b>, <b>6</b>), [3,3′-Co­(1,2-C₂B₉H₁₁)₂]⁻ (<b>7</b>, <b>8</b>), and [3,3′-Fe­(1,2-C₂B₉H₁₁)₂]⁻ (<b>9</b>) anions have been readily synthesized from <i>meso</i>-(4-hydroxyphenyl)-4,4-difluoro-4-bora-3<i>a</i>,4<i>a</i>-diaza-<i>s</i>-indacene (BODIPY <b>4</b>), and their structure and photoluminescence properties have been assessed. Linking anionic boron clusters to the BODIPY (<b>4</b>) does not alter significantly the luminescent properties of the final fluorophores, showing all of them similar emission fluorescent quantum yields (3–6%). Moreover, the cytotoxicity and cellular uptake of compounds <b>5</b>–<b>9</b> have been analyzed <i>in vitro</i> at different concentrations of B (5, 50, and 100 μg B/mL) using HeLa cells. At the lowest concentration, none of the compounds shows cytotoxicity and they are successfully internalized by the cells, especially compounds <b>7</b> and <b>8</b>, which exhibit a strong cytoplasmic stain indicating an excellent internalization efficiency. To the best of our knowledge, these are the first BODIPY-anionic boron cluster conjugates developed as fluorescent dyes aiming at prospective biomedical applications. Furthermore, the cellular permeability of the starting BODIPY (<b>4</b>) was improved after the functionalization with boron clusters. The exceptional cellular uptake and intracellular boron release, together with the fluorescent and biocompatibility properties, make compounds <b>7</b> and <b>8</b> good candidates for <i>in vitro</i> cell tracking