Roberto González‐Gómez

Cobalt‐based metallacarboranes have emerged as potential candidates for cancer treatment owing to their unique structural properties. In this study, a biocompatible delivery platform is developed by noncovalently incorporating cobalt metallacarborane (CoSAN) into hyaluronic acid (HA) functionalized with lysine (Lys). HA‐Lys 2 enables the electrostatic interaction of CoSAN while retaining its cytotoxic activity, as confirmed by cellular assays using MDA‐MB‐231 triple‐negative breast cancer cells. Elemental mapping via energy‐dispersive X‐ray spectroscopy (EDX) confirms the successful and homogeneous incorporation of CoSAN to lead HA‐Lys‐CoSAN 3 , and the composite is further characterized using diffusion‐ordered nuclear magnetic resonance (NMR) spectroscopy (DOSY). Stimulated Raman scattering (SRS) microscopy data demonstrate comparable cellular uptake in MDA‐MB‐231 cells of free and HA‐loaded CoSAN. Additionally, release studies under physiologically relevant conditions show a sustained release profile over 24 h with pH dependency to mimic normal and tumor microenvironments. The present study describes a viable method for integrating metallacarboranes into a polymeric drug delivery system without compromising their anticancer properties, thereby advancing their potential for future therapeutic use.

Porous materials have promising characteristics, including tuneable chemical and optical properties, which can be further expanded by their metalation. Yet, structural mapping of metalated covalent organic frameworks is a key challenge to overcome.

Studying the photophysical properties of ruthenium nanoparticles decorated with fluorescent pyrene-labelled dendrons has revealed very efficient fluorescence quenching, making these materials potentially interesting for photocatalytic applications.

Covalent and metal‐organic frameworks (COFs and MOFs) have shown great promise in light‐driven processes mainly due to their ligand‐to‐metal charge‐separation properties, as well as having access to a diverse range of photoactive metalloligands and organic linkers. However, both frameworks present individual drawbacks that can potentially be avoided by combining both systems (metal and covalent) to produce metal‐covalent organic frameworks (MCOFs), exhibiting the advantages of both material types. Yet, due to their poor crystallinity, the understanding of the structure‐properties relation of MCOFs remains unclear. Herein, we report photoactive linkers in the form of a [Ru(tpy) ₂ ] ²⁺ (tpy: 2,2′,6,2″‐terpyridine) complex which covalently binds to a luminescent pyrene core to yield a new, photoactive Schiff‐base MCOF. The structure, thermal, electronic, and optical properties of this novel material have been exhaustively characterized by a wide range of microscopy, spectroscopic, and computational methods. This combined experimental and computational work represents a significant step toward the fundamental understanding of the photoactive units within the framework, their hierarchical arrangement and interactions with substrates, which is essential for the future design of efficient photocatalytic materials.

Recentstudies toward finding more efficient ruthenium metalloligands for photocatalysis applications have shown that the derivatives of the linear [Ru(dqp)₂]²⁺ (dqp: 2,6-di(quinolin-8-yl)-pyridine) complexes hold significant promise due to their extended emission lifetime in the μs time scale while retaining comparable redox potential, extinction coefficients, and absorption profile in the visible region to [Ru(bpy)₃]²⁺ (bpy: 2,2'-bipyridine) and [Ru(tpy)₂]²⁺ (tpy: 2,2':6',2″-terpyridine) complexes. Nevertheless, its photostability in aqueous solution needs to be improved for its widespread use in photocatalysis. Carbon-based supports have arisen as potential solutions for improving photostability and photocatalytic activity, yet their effect greatly depends on the interaction of the metal complex with the support. Herein, we present a strategy for obtaining Ru-polypyridyl complexes covalently linked to aminated reduced graphene oxide (rGO) to generate novel materials with long-term photostability and increased photoactivity. Specifically, the hybrid Ru(dqp)@rGO system has shown excellent photostable behavior during 24 h of continual irradiation, with an enhancement of 10 and 15% of photocatalytic dye degradation in comparison with [Ru(dqp)₂]²⁺ and Ru(tpy)@rGO, respectively, as well as remarkable recyclability. The presented strategy corroborates the potential of [Ru(dqp)₂]²⁺ as an interesting photoactive molecule to produce more advantageous light-active materials by covalent attachment onto carbon-based supports.

A luminescent ruthenium complex bearing two 2,6‐di(quinolin‐8‐yl)‐pyridine carboxylic acid (dqpCOOH) ligands has been successfully synthesised and fully characterised. The new metalloligand has been coordinated to zinc ions through the terminal carboxylate groups using a one‐step solvothermal method, to give a multimetallic photoactive 1D coordination polymer, Ru−(dqpCOO)−Zn−(OOCH)₂. Through use of X‐ray crystallography, advanced microscopy techniques as well as photophysical studies, we have extensively characterised the coordination polymer. The optical properties of the ruthenium complex and corresponding coordination polymer show that the material experiences a dramatic increase in photostability compared to the free parent metalloligand, in solution. Electrochemical measurements of the coordination polymer also confirm the Ru^II/Ru^III redox couple is maintained in the polymeric network. The development of this material gives a new strategy in the design of novel photoactive materials as multimetallic building blocks for their use in light‐based applications.