arXiv subjects

Lorenzo Donà

Publications and source records attributed to Lorenzo Donà.

5 recordsLinked to original sources

arXiv2026

Elucidating Guest-Host Mechanisms in ZIF-L for Tuneable Highly Luminescent 2D Materials

3D metal-organic frameworks (MOFs) are well known effective hosts for luminescent guests that improve tuneability, photostability and material fabricability. 2D guest@MOF systems, while less explored, offer competitive advantages over 3D guest@MOF systems due to their optical transparency, inter-layer spacing, and vertical thinness. This work examines luminescent organic dyes@ZIF-L to establish the underlying mechanisms of guest incorporation in ZIF-L and demonstrate the advantages of the 2D ZIF-L architecture for the material's functional luminescence. Analysing a case study system, fluorescein@ZIF-L (F@ZIF-L), using nanoscale FTIR, diffraction, and topology mapping, confirmed that fluorescein (F) resided in the ZIF-L framework cavities. Supported by surface energy simulations, the extent of guest incorporation was found to be indicated by a morphological continuum, from the characteristic leaf-shaped ZIF-L to rectangular F@ZIF-L. By modifying synthesis temperature and solvent ratios, the luminescent properties of F@ZIF-L could be rationally tuned in terms of guest loading (% mol) and arrangement (i.e. guest monomer to aggregate ratio). When optimised, F@ZIF-L exhibited tuneable emission chromaticity, 99.7% photoluminescent quantum yield, minimal guest leaching in solution over 12 months, and high photostability. Perylene@ZIF-L exhibited unique white light emitting properties, with CIE coordinates (0.33, 0.34) arising from a combination of yellow alpha-phase excimer and blue monomeric perylene emission. Finally, oriented luminescent thin films of guest@ZIF-L materials were grown on malleable Zn foils, demonstrating an in situ fabrication technique. Together, the work highlights the potential for luminescent dye@ZIF-L systems in developing tuneable and resilient luminescent components of next-generation optoelectronics, sensors, and lighting systems.

cond-mat.mtrl-sci↗

arXiv2026

Topology-Controlled Phonon Dielectric Response Beyond Density Scaling in Metal-Organic Frameworks

Effective-medium theory treats material porosity as passive dilution. Using ab initio density functional theory and high-resolution synchrotron terahertz (THz) spectroscopy on isochemical zeolitic-imidazolate frameworks, we show that while the electronic permittivity obeys Clausius-Mossotti density scaling, the phonon contribution violates the conventional density scaling rules. Identical Born charges rule out the role of local chemistry. Instead, the framework connectivity localizes the THz response, where the coherency of phonon eigenvectors determines the mode-effective charges. Long-range architecture of framework topology ubiquitous in metal-organic frameworks is therefore a dielectric degree of freedom beyond the density scaling of conventional solids.

cond-mat.mtrl-sci↗

arXiv2021

Tunable Fluorescein-Encapsulated Zeolitic Imidazolate Framework-8 Nanoparticles for Solid-State Lighting

A series of fluorescein-encapsulated zeolitic imidazolate framework-8 (fluorescein@ZIF-8) luminescent nanoparticles with a scalable guest loading has been fabricated and characterized. The successful encapsulation of the organic dye (fluorescein) is supported by both experimental evidence and theoretical simulations. The measured optical band gap is found to be comparable with the computed values of a hypothetical guest-host system. Isolated monomers and aggregates species of fluorescein confined in ZIF-8 nanocrystals have been systematically investigated through fluorescence lifetime spectroscopy. The quantum yield (QY) of the obtained solid-state materials is particularly high (QY~98%), especially when the concentration of the fluorescein guest is low. Combining a blue LED chip and a thin photoactive film of fluorescein@ZIF-8, we demonstrate a device with good optical tunability for multicolor and white light emissions. Additionally, we show that the fluorescein@ZIF-8 nanoparticles exhibit an improved photostability due to the shielding effect conferred by the nanoconfinement of host framework, making them promising candidates for practical applications such as solid-state lighting, photonics, and optical communications.

cond-mat.mtrl-sci↗

arXiv2021

Defects in ZIF-8 crystallization and their impact on mechanical properties

The growth process of metal-organic frameworks (MOFs) defines their properties for functional applications. However, it is very plausible that defects may occur during the crystallization of even seemingly perfect MOFs, such as ZIF-8, and yet, direct probing of such structural defects has been challenging due to the lack of techniques to locally examine individual nanocrystals. Now, we directly study local defects - such as missing linkers or metal vacancies - in ZIF-8 nano- and microcrystals with near-field infrared nanospectroscopy combined with density function theory calculations. We have tracked the chemical changes during crystallization and found that structural defects like zinc-rich regions gradually disappear with the ripening of the crystals, while missing linker defects prevail. The resulting open metal sites reduce the Young's modulus, as measured with tip force microscopy and supported by theoretical modelling, but also open the door for defect engineering to tune the adsorption and catalytic performance of ZIF-8.

cond-mat.mtrl-sci↗

arXiv2019

Impact of pressure and temperature on the broadband dielectric response of the HKUST-1 metal-organic framework

Herein we employed high-resolution spectroscopic techniques in combination with periodic ab initio density functional theory (DFT) calculations to establish the different polarization processes for a porous copper-based MOF, termed HKUST-1. We used alternating current measurements to determine its dielectric response between 4 Hz and 1.5 MHz where orientational polarization is predominant, while synchrotron infrared (IR) reflectance was used to probe the far-IR, mid-IR, and near-IR dielectric response across the 1.2 THz to 150 THz range (ca. 40 - 5000 cm^-1) where vibrational and optical polarizations are principal contributors to its dielectric permittivity. We demonstrate the role of pressure on the evolution of broadband dielectric response, where THz vibrations reveal distinct blue and red shifts of phonon modes from structural deformation of the copper paddle-wheel and the organic linker, respectively. We also investigated the effect of temperature on dielectric constants in the MHz region pertinent to microelectronics, to study temperature-dependent dielectric losses via dissipation in an alternating electric field. The DFT calculations offer insights into the physical mechanisms responsible for dielectric transitions observed in the experiments and enable us to explain the frequency shifts phenomenon detected under pressure. Together, the experiments and theory have enabled us to glimpse into the complex dielectric response and mechanisms underpinning a prototypical MOF subject to pressure, temperature, and vast frequencies.

cond-mat.mtrl-sci↗