Yoan Hidalgo-Rosa

This work presents a systematic theoretical investigation of 16 hexa-substituted Zn(II) phthalocyanines functionalized with different anchoring groups and bulky substituents, using density functional theory (DFT) and time-dependent DFT (TD-DFT), at both molecular and periodic levels. The objective is to elucidate the combined effect of anchoring groups and substituents on the structural, electronic, optical, and interfacial properties relevant to dye-sensitized solar cells (DSSCs). The results show that all systems preserve a nearly planar macrocycle, although bulkier substituents induce slight distortions that may reduce aggregation effects. The optical absorption spectra exhibit strong absorption in the visible–near-infrared region (up to 827 nm), with both substituents and anchoring groups significantly influencing the position and intensity of the Q bands. Electron-injection analysis (ΔGinj) indicates favorable energetic alignment between the excited states of the dyes and the TiO2 conduction band, with values ranging from -0.81 to -1.04 eV depending on the anchoring group. Charge transfer and electron–hole distribution analysis confirm efficient intramolecular charge separation toward the anchoring moiety. Adsorption studies reveal that the nature of the anchoring group strongly affects binding strength, interfacial electronic coupling, and charge transfer at the dye–TiO2 interface. Counterpoise-corrected interaction energies range from -4.25 to -4.66 eV. In particular, alternative anchoring groups, such as thiophene-based cyanoacrylic acid and ethynyl-linked benzothiadiazole carboxylic acid, exhibit improved adsorption characteristics compared to conventional carboxylic groups. Density of states analysis further highlights the role of substituents in modulating the electronic structure and facilitating charge injection. Overall, this study demonstrates the synergistic effect of anchoring groups and bulky substituents in tuning the performance of Zn(II) phthalocyanine-based sensitizers, providing useful design guidelines for the development of more efficient DSSCs.

The porous structure of metal-organic framework UiO-66 present a suitable scaffold to design drug delivery devices that improve the administration of drugs with low solubility and low absorption such the calcium-channel-blockers.

Postsynthetic modification (PSM) as lanthanide incorporation combined with transition metal codoping has proven to be a highly effective strategy for significantly enhancing the luminescence efficiency of metal-organic framework (MOF)-based materials. In this study, we investigated a series of luminescent materials: Ln³⁺/M@UiO-66-(COOH)₂ (M = Cd²⁺, Ag⁺; Ln³⁺ = Eu³⁺, Tb³⁺). These MOFs hold 1,2,4,5-benzenetetracarboxylic acid (H₄btec) as organic linkers, which provide coordination sites that facilitate the incorporation of codopant metal ions into the MOF structure. The primary goal of this work is to elucidate the photophysical mechanisms underlying energy sensitization and emission pathways in these systems, with special emphasis on the influence of transition metal ions on the excited-state dynamics and energy transfer to the Ln³⁺ emitting centers. The results obtained using multiconfiguration calculations (CASSCF/NEVPT2) and time-dependent DFT (TDDFT) reveal that the presence of Cd²⁺ and Ag⁺ ions stabilizes the triplet state T₁ of the linker, favoring a more efficient energy transfer to the excited states of Eu³⁺. This stabilization allows direct sensitization to the ⁵D₂ level, instead of ⁵D₄ as occurs in the absence of codopants, which reduces energy losses associated with nonradiative processes and results in a significant improvement in Eu³⁺ luminescence. Building upon these findings and to broaden the scope of our investigation, we extended the study to a new luminescent sensor where Eu³⁺ was replaced by Tb³⁺. The new Tb³⁺-based system exhibited an even higher luminescence efficiency, which can be attributed to the direct sensitization of the ⁵D₄ excited state, from which radiative deactivation occurs efficiently. Overall, this study demonstrates that combining lanthanide doping with transition metal codoping allows for rational modulation of excited-state processes, providing a strategic framework for the design of high-performance luminescent MOF-based sensors.

In this report, a quantum chemical theoretical protocol was used to elucidate the detection principle of the turn-on luminescence mechanism in a modified MOF labeled as Ln³⁺@UiO-66-(COOH)₂ (Ln³⁺ = Eu³⁺ or Tb³⁺).

Cross-aldol condensation reaction study using a family of UiO-66 MOFs between benzaldehyde and acetone to produce benzalacetone.

Metal–organic frameworks (MOFs) are hybrid organic–inorganic porous materials composed of metal cations and polydentate organic ligands, forming high porosity and surface areas modular architectures, which could be applied for hydrogen technologies.

MOF-808-SO₄-M (M = Zr(iv), Hf(iv)) is obtained by post-synthetic modification (PSM) of MOF-808-M. The introduction of superacidity significantly improves its catalytic activity in the acetalization of benzaldehyde.