J Perego

Bio: J Perego is an academic researcher from University of Milano-Bicocca. The author has contributed to research in topics: Materials science & Polymer. The author has an hindex of 8, co-authored 14 publications receiving 164 citations.

Composite fast scintillators based on high-Z fluorescent metal–organic framework nanocrystals

Abstract: Scintillators, materials that produce light pulses upon interaction with ionizing radiation, are widely employed in radiation detectors. In advanced medical-imaging technologies, fast scintillators enabling a time resolution of tens of picoseconds are required to achieve high-resolution imaging at the millimetre length scale. Here we demonstrate that composite materials based on fluorescent metal–organic framework (MOF) nanocrystals can work as fast scintillators. We present a prototype scintillator fabricated by embedding MOF nanocrystals in a polymer. The MOF comprises zirconium oxo-hydroxy clusters, high-Z linking nodes interacting with the ionizing radiation, arranged in an orderly fashion at a nanometric distance from 9,10-diphenylanthracene ligand emitters. Their incorporation in the framework enables fast sensitization of the ligand fluorescence, thus avoiding issues typically arising from the intimate mixing of complementary elements. This proof-of-concept prototype device shows an ultrafast scintillation rise time of ~50 ps, thus supporting the development of new scintillators based on engineered fluorescent MOF nanocrystals. Composites of fluorescent metal–organic framework nanocrystals in a polymer are exploited to create fast scintillators with a rise time of about 50 ps.

Fast motion of molecular rotors in metal-organic framework struts at very low temperatures

Abstract: The solid state is typically not well suited to sustaining fast molecular motion, but in recent years a variety of molecular machines, switches and rotors have been successfully engineered within porous crystals and on surfaces Here we show a fast-rotating molecular rotor within the bicyclopentane–dicarboxylate struts of a zinc-based metal–organic framework—the carboxylate groups anchored to the metal clusters act as an axle while the bicyclic unit is free to rotate The three-fold bipyramidal symmetry of the rotator conflicts with the four-fold symmetry of the struts within the cubic crystal cell of the zinc metal–organic framework This frustrates the formation of stable conformations, allowing for the continuous, unidirectional, hyperfast rotation of the bicyclic units with an energy barrier of 62 cal mol−1 and a high frequency persistent for several turns even at very low temperatures (1010 Hz below 2 K) Using zirconium instead of zinc led to a different metal cluster–carboxylate coordination arrangement in the resulting metal–organic framework, and much slower rotation of the bicyclic units Molecular rotors have been engineered within the bicyclopentane–dicarboxylate struts of a metal–organic framework—the bicyclic unit is the rotator and the carboxylate groups serve as the stator In a zinc-based metal–organic framework, the crossed conformation of the strut–metal nodes enables fast rotation of the bicyclic moiety, but in the corresponding zirconium metal–organic framework a change in the conformation results in much slower rotation

Modulation of porosity in a solid material enabled by bulk photoisomerization of an overcrowded alkene

Abstract: The incorporation of photoswitchable molecules into solid-state materials holds promise for the fabrication of responsive materials, the properties of which can be controlled on-demand However, the possible applications of these materials are limited due to the restrictions imposed by the solid-state environment on the incorporated photoswitches, which render the photoisomerization inefficient Here we present responsive porous switchable framework materials based on a bistable chiroptical overcrowded alkene incorporated in the backbone of a rigid aromatic framework As a consequence of the high intrinsic porosity, the resulting framework readily responds to a light stimulus, as demonstrated by solid-state Raman and reflectance spectroscopies Solid-state 13C NMR spectroscopy highlights an efficient and quantitative bulk photoisomerization of the incorporated light-responsive overcrowded olefins in the solid material Taking advantage of the quantitative photoisomerization, the porosity of the framework and the consequent gas adsorption can be reversibly modulated in response to light and heat Despite numerous potential applications, the development of light-responsive solid materials based on molecular photoswitches is impeded by the low efficiency of photoisomerization in the solid environment Now a robust, solid porous material made from tetraphenylmethane and a photoswitchable overcrowded alkene exhibits nearly quantitative photoisomerization in the bulk and in photomodulation of gas uptake

Porous 3D polymers for high pressure methane storage and carbon dioxide capture

Abstract: High surface area 3D polymers represent one of the most promising classes of porous materials because of their high gas uptake and stability to thermal and chemical degradation. A series of porous organic polymers with aromatic building units have been synthesized and compared to explore their high-pressure performance as adsorbents of gases of relevant importance for energy and the environment. Particular attention was paid to methane storage up to pressures as high as 180 bar at ambient temperature. Porous polymers were prepared starting from a wide choice of spatially expanded aromatic monomers: a systematic change in the number of rings, variable size and shape was taken under consideration. The high number of rings (up to 6), which act as multiple reactive sites and form a number of connections between the multi-dentate nodes, result in an extensive cross-linked framework. Condensation was obtained by two alternative synthetic routes, viz., Yamamoto cross-coupling and Friedel–Crafts alkylation reactions. The structural characteristics and high stability of the porous polymers, even to mechanical compression, were carefully determined by several methods, including 1D and 2D solid state NMR, FT IR and thermal analyses. The CH4 uptake in the porous polymers allowed an understanding of the incremental response to pressure, up to extremely high values, and the exploitation of the extensive pressure range to customize the gas adsorption/desorption cycles for storage and transportation. Owing to the notable presence of large mesopores and network flexibility, combined with high surface area, a remarkable gain at high pressure was achieved, ensuring a highly competitive uptake/delivery efficiency. At 180 bar, adsorption values up to 445 cm3 STP g−1 were measured for porous organic polymers such as carbazolyl- and triptycene-based materials. The benchmark of these materials PAF1 reaches the value of 916 cm3 STP g−1 of adsorbed CH4, exceeding the performance of most of the best performing MOFs, COFs and activated carbons. CO2 and N2 adsorption isotherms collected at room temperature enabled the assessment of the suitability of such polymer networks for CO2 selective separation and capture. In summary, the in-depth and extensive comparative screening within this class of materials up to high pressures provides the necessary parameters for further synthetic and applicative work.

Engineering Porous Emitting Framework Nanoparticles with Integrated Sensitizers for Low‐Power Photon Upconversion by Triplet Fusion

Abstract: The conversion of low-energy light into photons of higher energy based on sensitized triplet-triplet annihilation (sTTA) upconversion is emerging as the most promising wavelength-shifting methodology because it operates efficiently at excitation powers as low as the solar irradiance. However, the production of solid-state upconverters suited for direct integration in devices is still an ongoing challenge owing to the difficulties concerning the organization of two complementary moieties, the triplet sensitizer, and the annihilator, which must interact efficiently. This problem is solved by fabricating porous fluorescent nanoparticles wherein the emitters are integrated into robust covalent architectures. These emitting porous aromatic framework (ePAF) nanoparticles allow intimate interaction with the included metallo-porphyrin as triplet sensitizers. Remarkably, the high concentration of framed chromophores ensures hopping-mediated triplet diffusion required for TTA, yet the low density of the framework promotes their high optical features without quenching effects, typical of the solid state. A green-to-blue photon upconversion yield as high as 15% is achieved: a record performance among annihilators in a condensed phase. Furthermore, the engineered ePAF architecture containing covalently linked sensitizers produces full-fledge solid-state bicomponent particles that behave as autonomous nanodevices.

Emerging trends in porous materials for CO2 capture and conversion

Abstract: The presence of an excessive concentration of CO2 in the atmosphere needs to be curbed with suitable measures including the reduction of CO2 emissions at stationary point sources such as power plants through carbon capture technologies and subsequent conversion of the captured CO2 into non-polluting clean fuels/chemicals using photo and/or electrocatalytic pathways. Porous materials have attracted much attention for carbon capture and in the recent past; they have witnessed significant advancements in their design and implementation for CO2 capture and conversion. In this context, the emerging trends in major porous adsorbents such as MOFs, zeolites, POPs, porous carbons, and mesoporous materials for CO2 capture and conversion are discussed. Their surface texture and chemistry, and the influence of various other features on their efficiency, selectivity, and recyclability for CO2 capture and conversion are explained and compared thoroughly. The scientific and technical advances on the material structure versus CO2 capture and conversion provide deep insights into designing effective porous materials. The review concludes with a summary, which compiles the key challenges in the field, current trends and critical challenges in the development of porous materials, and future research directions combined with possible solutions for realising the deployment of porous materials in CO2 capture and conversion.

Porous Aromatic Frameworks (PAFs)

Abstract: Porous aromatic frameworks (PAFs) represent an important category of porous solids. PAFs possess rigid frameworks and exceptionally high surface areas, and, uniquely, they are constructed from carbon-carbon-bond-linked aromatic-based building units. Various functionalities can either originate from the intrinsic chemistry of their building units or are achieved by postmodification of the aromatic motifs using established reactions. Specially, the strong carbon-carbon bonding renders PAFs stable under harsh chemical treatments. Therefore, PAFs exhibit specificity in their chemistry and functionalities compared with conventional porous materials such as zeolites and metal organic frameworks. The unique features of PAFs render them being tolerant of severe environments and readily functionalized by harsh chemical treatments. The research field of PAFs has experienced rapid expansion over the past decade, and it is necessary to provide a comprehensive guide to the essential development of the field at this stage. Regarding research into PAFs, the synthesis, functionalization, and applications are the three most important topics. In this thematic review, the three topics are comprehensively explained and aptly exemplified to shed light on developments in the field. Current questions and a perspective outlook will be summarized.

Publisher's Note: Upconversion-induced fluorescence in multicomponent systems: Steady-state excitation power threshold

Abstract: We have analyzed the dynamics of the upconversion-induced delayed fluorescence for a model multicomponent organic system, in which high concentrations of triplet states can be sustained in steady-state conditions. At different excitation powers, two regimes have been identified depending on the main deactivation channel for the triplets, namely, the spontaneous decay and the bimolecular annihilation. The excitation power density at which triplet bimolecular annihilation becomes dominant is the threshold $({I}_{\text{th}})$ to have efficient upconversion generation. The simple equation obtained for ${I}_{\text{th}}$ allows us to predict the theoretical efficiency of a generic system on the basis of few parameters of the constituent molecules.

Organic molecular sieve membranes for chemical separations.

Abstract: Molecular separations that enable selective transport of target molecules from gas and liquid molecular mixtures, such as CO2 capture, olefin/paraffin separations, and organic solvent nanofiltration, represent the most energy sensitive and significant demands. Membranes are favored for molecular separations owing to the advantages of energy efficiency, simplicity, scalability, and small environmental footprint. A number of emerging microporous organic materials have displayed great potential as building blocks of molecular separation membranes, which not only integrate the rigid, engineered pore structures and desirable stability of inorganic molecular sieve membranes, but also exhibit a high degree of freedom to create chemically rich combinations/sequences. To gain a deep insight into the intrinsic connections and characteristics of these microporous organic material-based membranes, in this review, for the first time, we propose the concept of organic molecular sieve membranes (OMSMs) with a focus on the precise construction of membrane structures and efficient intensification of membrane processes. The platform chemistries, designing principles, and assembly methods for the precise construction of OMSMs are elaborated. Conventional mass transport mechanisms are analyzed based on the interactions between OMSMs and penetrate(s). Particularly, the 'STEM' guidelines of OMSMs are highlighted to guide the precise construction of OMSM structures and efficient intensification of OMSM processes. Emerging mass transport mechanisms are elucidated inspired by the phenomena and principles of the mass transport processes in the biological realm. The representative applications of OMSMs in gas and liquid molecular mixture separations are highlighted. The major challenges and brief perspectives for the fundamental science and practical applications of OMSMs are tentatively identified.