Scintillation Properties of CsPbBr3 Nanocrystals Prepared by Ligand-Assisted Reprecipitation and Dual Effect of Polyacrylate Encapsulation toward Scalable Ultrafast Radiation Detectors.

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

Orthogonal Photoswitching in a Porous Organic Framework.

The development of photoresponsive systems with non-invasive orthogonal control by distinct wavelengths of light is still in its infancy. In particular, the design of photochemically triggered-orthogonal systems integrated into solid materials that enable multiple dynamic control over their properties remains a longstanding challenge. Here, we report the orthogonal and reversible control of two types of photoswitches in an integrated solid porous framework, that is, visible-light responsive o-fluoroazobenzene and nitro-spiropyran motifs. The properties of the constructed material can be selectively controlled by different wavelengths of light thus generating four distinct states providing a basis for dynamic multifunctional materials. Solid-state NMR spectroscopy demonstrated the selective transformation of the azobenzene switch in the bulk, which in turn modulates N2 and CO2 adsorption.

Solid State Machinery of Multiple Dynamic Elements in a Metal-Organic Framework.

Engineering coordinated rotational motion in porous architectures enables the fabrication of molecular machines in solids. A flexible two-fold interpenetrated pillared Metal-Organic Framework precisely organizes fast mobile elements such as bicyclopentane (BCP) (107  Hz regime at 85 K), two distinct pyridyl rotors and E-azo group involved in pedal-like motion. Reciprocal sliding of the two sub-networks, switched by chemical stimuli, modulated the sizes of the channels and finally the overall dynamical machinery. Actually, iodine-vapor adsorption drives a dramatic structural rearrangement, displacing the two distinct subnets in a concerted piston-like motion. Unconventionally, BCP mobility increases, exploring ultra-fast dynamics (107  Hz) at temperatures as low as 44 K, while the pyridyl rotors diverge into a faster and slower dynamical regime by symmetry lowering. Indeed, one pillar ring gained greater rotary freedom as carried by the azo-group in a crank-like motion. A peculiar behavior was stimulated by pressurized CO2, which regulates BCP dynamics upon incremental site occupation. The rotary dynamics is intrinsically coupled to the framework flexibility as demonstrated by complementary experimental evidence (multinuclear solid-state NMR down to very low temperatures, synchrotron radiation XRD, gas sorption) and computational modelling, which helps elucidate the highly sophisticated rotor-structure interplay.

Benchmark Dynamics of Dipolar Molecular Rotors in Fluorinated Metal-Organic Frameworks.

Fluorinated Metal-Organic Frameworks (MOFs), comprising a wheel-shaped ligand with geminal rotating fluorine atoms, produced benchmark mobility of correlated dipolar rotors at 2 K, with practically null activation energy (Ea =17 cal mol-1 ). 1 H T1 NMR revealed multiple relaxation phenomena due to the exchange among correlated dipole-rotor configurations. Synchrotron radiation X-ray diffraction at 4 K, Density Functional Theory, Molecular Dynamics and phonon calculations showed the fluid landscape and pointed out a cascade mechanism converting dipole configurations into each other. Gas accessibility, shown by hyperpolarized-Xe NMR, allowed for chemical stimuli intervention: CO2 triggered dipole reorientation, reducing their collective dynamics and stimulating a dipole configuration change in the crystal. Dynamic materials under limited thermal noise and high responsiveness enable the fabrication of molecular machines with low energy dissipation and controllable dynamics.

Collective dynamics of molecular rotors in periodic mesoporous organosilica: a combined solid-state 2H-NMR and molecular dynamics simulation study.

Molecular rotors offer a platform to realize controlled dynamics and modulate the functions of solids. The motional mechanisms in arrays of rotors have not been explored in depth. Crystal-like porous organosilicas, comprising p-phenylene rotators pivoted onto a siloxane scaffold, were modelled using molecular dynamics (MD) simulations. Long simulations, on a microsecond scale, allowed to follow the reorientation statistics of rotor collections and single out group configurations and frequency distributions as a function of temperature. The motions observed in the MD simulations support a multiple-site model for rotor reorientations. Computed motional frequencies revealed a complex rotatory phenomenon combining an ultra-fast libration motion (oscillation up to 30°) with a slow and fast 180° flip reorientation. Adopting a multiple-site model provides a more accurate simulation of the 2H-NMR spectra and a rationalization of their temperature dependence. In particular, rotators endowed with distinct rates could be explained by the presence of slower rings locked in a T-shaped conformation.

Cascade Dynamics of Multiple Molecular Rotors in a MOF: Benchmark Mobility at a Few Kelvins and Dynamics Control by CO2.

Achieving sophisticated juxtaposition of geared molecular rotors with negligible energy-requirements in solids enables fast yet controllable and correlated rotary motion to construct switches and motors. Our endeavor was to realize multiple rotors operating in a MOF architecture capable of supporting fast motional regimes, even at extremely cold temperatures. Two distinct ligands, 4,4'-bipyridine (bipy) and bicyclo[1.1.1]pentanedicarboxylate (BCP), coordinated to Zn clusters fabricated a pillar-and-layer 3D array of orthogonal rotors. Variable temperature XRD, 2H solid-echo, and 1H T1 relaxation NMR, collected down to a temperature of 2 K revealed the hyperfast mobility of BCP and an unprecedented cascade mechanism modulated by distinct energy barriers starting from values as low as 100 J mol-1 (24 cal mol-1), a real benchmark for complex arrays of rotors. These rotors explored multiple configurations of conrotary and disrotary relationships, switched on and off by thermal energy, a scenario supported by DFT modeling. Furthermore, the collective bipy-ring rotation was concerted with the framework, which underwent controllable swinging between two arrangements in a dynamical structure. A second way to manipulate rotors by external stimuli was the use of CO2, which diffused through the open pores, dramatically changing the global rotation mechanism. Collectively, the intriguing gymnastics of multiple rotors, devised cooperatively and integrated into the same framework, gave the opportunity to engineer hypermobile rotors (107 Hz at 4 K) in machine-like double ligand MOF crystals.

Molecular Rotors in a Metal-Organic Framework: Muons on a Hyper-Fast Carousel.

Using muon-spin spectroscopy, we study the exceptional dynamical properties of rotating molecular struts engineered within a Zn-based metal-organic framework at cryogenic temperatures, where the internal motions of almost any other organic substance are quenched. Muon-spin spectroscopy is particularly suited for this aim, as the experimental evidence suggests several implantation sites for the muons, among which at least one directly onto the rotating moiety. The dynamics of the molecular rotors are characterized by the exceptionally low activation energy EA ∼ 30 cal mol-1. At the same time, we evidence a highly unusual temperature dependence of the dipolar interaction of muons with nuclear magnetic moments on the rotors, suggesting a complex influence of the rotations on the muon implantation and diffusion.

Anionic Polymerization in Porous Organic Frameworks: A Strategy to Fabricate Anchored Polymers and Copolymers.

An anionic mechanism is used to create polymers and copolymers as confined to, or anchored to, high-surface-area porous nanoparticles. Linear polymers with soft and glassy chains, such as polyisoprene and polymethylmethacrylate, were produced by confined anionic polymerization in 3D networks of porous aromatic frameworks. Alternatively, multiple anions were generated on the designed frameworks which bear removal protons at selected positions, and initiate chain propagation, resulting in chains covalently connected to the 3D network. Such growth can continue outside the pores to produce polymer-matrix nanoparticles coated with anchored chains. Sequential reactions were promoted by the living character of this anionic propagation, yielding nanoparticles that were covered by a second polymer anchored by anionic block copolymerization. The intimacy of the matrix and the grown-in polymers was demonstrated by magnetization transfer across the interfaces in 2D 1 H-13 C-HETCOR NMR spectra.

Confined Polymerization in Highly Ordered Mesoporous Organosilicas.

Hybrid mesoporous organosilica exhibiting crystal-like order in the walls provided an ideal channel reaction vessel for the confined polymerization of acrylonitrile (PAN). The resulting high-molecular-mass PAN fills the channels at high yield and forms an ordered nanostructure of polymer nanobundles enclosed into the hybrid matrix. The in situ thermal transformation of PAN into rigid polyconjugated and, eventually, into condensed polyaromatic carbon nanofibers, retains the periodic architecture. Simultaneously, the matrix evolves showing the fusion of the p-phenylene rings and the cleavage of carbonsilicon bonds: this gives rise to graphitic-carbon/silica nanocomposites containing hyper-oxydrylated silica nanophases. Interestingly, the 3D hexagonal mesostructure survives in the carbonaceous material. The exploitation of porous materials of high capacity and a hybrid nature, for polymerization in the confined state, followed by high temperature treatments, allowed us to achieve unique and precisely fabricated nanostructures, thus paving the way for the construction of fine-tuned electronic and light-harvesting materials.

Construction of Multi-Stimuli Responsive Highly Porous Switchable Frameworks by In Situ Solid-State Generation of Spiropyran Switches.

Stimuli-responsive molecular systems support within permanently porous materials offer the opportunity to host dynamic functions in multifunctional smart materials. However, the construction of highly porous frameworks featuring external-stimuli responsiveness, for example by light excitation, is still in its infancy. Here a general strategy is presented to construct spiropyran-functionalized highly porous switchable aromatic frameworks by modular and high-precision anchoring of molecular hooks and an innovative in situ solid-state grafting approach. Three spiropyran-grafted frameworks bearing distinct functional groups exhibiting various stimuli-responsiveness are generated by two-step post-solid-state synthesis of a parent indole-based material. The quantitative transformation and preservation of high porosity are demonstrated by spectroscopic and gas adsorption techniques. For the first time, a highly efficient strategy is provided to construct multi-stimuli-responsive, yet structurally robust, spiropyran materials with high pore capacity which is proved essential for the reversible and quantitative isomerization in the bulk as demonstrated by solid-state NMR spectroscopy. The overall strategy allows to construct dynamic materials that undergoes reversible transformation of spiropyran to zwitterionic merocyanine, by chemical and physical stimulation, showing potential for pH active control, responsive gas uptake and release, contaminant removal, and water harvesting.

Ultrafast and Radiation-Hard Lead Halide Perovskite Nanocomposite Scintillators.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

Phosphine Oxide Porous Organic Polymers Incorporating Cobalt(II) Ions: Synthesis, Characterization, and Investigation of H2 Production.

Suitably functionalized porous matrices represent versatile platforms to support well-dispersed catalytic centers. In the present study, porous organic polymers (POPs) containing phosphine oxide groups were fabricated to bind transition metals and to be investigated for potential electrocatalytic applications. Cross-linking of mono- and di-phosphine monomers with multiple phenyl substituents was subject to the Friedel-Crafts (F-C) reaction and the oxidation process, which generated phosphine oxide porous polymers with pore capacity up to 0.92 cm3/g and a surface area of about 990 m2/g. The formation of the R3P·BH3 borohydride adduct during synthesis allows to extend the library of phosphine-based monomeric entities when using FeCl3. The porous polymers were loaded with 0.8-4.2 w/w % of cobalt(II) and behaved as hydrogen evolution reaction (HER) catalysts with a Faradaic efficiency of up to 95% (5.81 × 10-5 mol H2 per 11.76 C) and a stable current density during repeated controlled potential experiments (CPE), even though with high overpotentials (0.53-0.68 V to reach a current density of 1 mA·cm-2). These studies open the way to the effectiveness of tailored phosphine oxide POPs produced through an inexpensive and ecofriendly iron-based catalyst and for the insertion of transition metals in a porous architecture, enabling electrochemically driven activation of small molecules.

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

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 6.2 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.

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

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.

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

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.