Quasi-thresholdless Photon Upconversion in Metal-Organic Framework Nanocrystals.

Photon upconversion based on sensitized triplet-triplet annihilation ( sTTA) is considered as a promising strategy for the development of light-managing materials aimed to enhance the performance of solar devices by recovering unused low-energy photons. Here, we demonstrate that, thanks to the fast diffusion of excitons, the creation of triplet pairs in metal-organic framework nanocrystals ( nMOFs) with size smaller than the exciton diffusion length implies a 100% TTA yield regardless of the illumination condition. This makes each nMOF a thresholdless, single-unit annihilator. We develop a kinetic model for describing the upconversion dynamics in a nanocrystals ensemble, which allows us to define the threshold excitation intensity  Ithbox required to reach the maximum conversion yield. For materials based on thresholdless annihilators, Ithbox is determined by the statistical distribution of the excitation energy among nanocrystals. The model is validated by fabricating a nanocomposite material based on nMOFs, which shows efficient upconversion under a few percent of solar irradiance, matching the requirements of real life solar technologies. The statistical analysis reproduces the experimental findings, and represents a general tool for predicting the optimal compromise between dimensions and concentration of nMOFs with a given crystalline structure that minimizes the irradiance at which the system starts to fully operate.

Highly Fluorescent Metal-Organic-Framework Nanocomposites for Photonic Applications.

Metal-organic frameworks (MOFs) are porous hybrid materials built up from organic ligands coordinated to metal ions or clusters by means of self-assembly strategies. The peculiarity of these materials is the possibility, according to specific synthetic routes, to manipulate both the composition and ligands arrangement in order to control their optical and energy-transport properties. Therefore, optimized MOFs nanocrystals (nano-MOFs) can potentially represent the next generation of luminescent materials with features similar to those of their inorganic predecessors, that is, the colloidal semiconductor quantum dots. The luminescence of fluorescent nano-MOFs is generated through the radiative recombination of ligand molecular excitons. The uniqueness of these nanocrystals is the possibility to pack the ligand chromophores close enough to allow a fast exciton diffusion but sufficiently far from each other preventing the aggregation-induced effects of the organic crystals. In particular, the formation of strongly coupled dimers or excimers is avoided, thus preserving the optical features of the isolated molecule. However, nano-MOFs have a very small fluorescence quantum yield (QY). In order to overcome this limitation and achieve highly emitting systems, we analyzed the fluorescence process in blue emitting nano-MOFs and modeled the diffusion and quenching mechanism of photogenerated singlet excitons. Our results demonstrate that the excitons quenching in nano-MOFs is mainly due to the presence of surface-located, nonradiative recombination centers. In analogy with their inorganic counterparts, we found that the passivation of the nano-MOF surfaces is a straightforward method to enhance the emission efficiency. By embedding the nanocrystals in an inert polymeric host, we observed a +200% increment of the fluorescence QY, thus recovering the emission properties of the isolated ligand in solution.

Applicability of MIL-101(Fe) as a cathode of lithium ion batteries.

MIL-101(Fe) was investigated as a cathode material of lithium ion batteries. A battery test reveals that MIL-101(Fe) shows a charge and discharge capacitance of 110 mA h g-1. It also showed reversible charge and discharge cycles and uptake of 0.62 Li/Fe after 100 cycles, which is the highest loading amount ever reported for the carboxylic MOFs. It also operates in the temperature range up to 350 °C and showed a good high thermal stability.

Hierarchical self-assembly of chiral complementary hydrogen-bond networks in water: reconstitution of supramolecular membranes.

Spontaneous formation of complementary hydrogen-bond pairs and their hierarchical self-assembly (reconstitution) into chiral supramolecular membranes are achieved in water by mixing amphiphilic pairs of glutamate-derived melamine 6 and ammonium-derivatized azobenzene cyanuric acid 4. Electron microscopy is used to observe formation of helical superstructures, which are distinct from the aggregate structures observed for each of the single components in water. In addition, a spectral blue-shift and induced circular dichroism (ICD) with exciton coupling are observed for the pi-pi* absorption of the azobenzene chromophores. These observations are consistent with the reconstitution of the hydrogen-bond-mediated supramolecular membrane 6-4. Spectral titration experiments indicate the stoichiometric integration of the complementary subunits with an association constant of 1.13 x 10(5) M(-1). This value is considerably larger than those reported for the artificial hydrogen-bonding complexes in aqueous media. The remarkable reconstitution efficiency is ascribed to the hydrophobically driven self-organization of the amphiphilic, linear hydrogen-bond networks in water. Molecular structure of the complementary subunits plays an important role in the complexation process since it is restricted by the photoisomerized cis-azobenzene subunit. On the other hand, thermally regenerated trans-isomer 4 undergoes facile complexation with the counterpart 6. The present reconstitution of supramolecular membranes provides the first example of complementary hydrogen-bond-directed formation of soluble, mesoscopic supramolecular assemblies in water.

Modulated structure of the pseudohexagonal InFe(1--x--4 delta)Ti(x+3 delta)O(3+x/2) (x = 0.61) composite crystal.

The structure of pseudohexagonal-type InFe(1--x--4 delta)Ti(x+3 delta)O(3+x/2) (x = 0.61, delta = 0.04), indium iron titanium oxide, was refined on the basis of a four-dimensional superspace group. The crystal has a compositely modulated structure consisting of two orthorhombic subsystems mutually incommensurate in b. The first subsystem InFe(1-x-4 delta)Ti(x+3 delta)O(2) has a delafossite structure with lattice parameters a = 5.835 (3), b(1) = 3.349 (1) and c = 12.082 (7) A. The second subsystem with b(2) = 2.568 (6) A consists of O atoms. The superspace group of the overall structure is Ccmm(1, 1.305, 0)s00, which can be converted to Amam(0, 0, 0.305)0s0 (No. 63.8). Refinement on 1105 unique reflections converged to R = 0.0303 and wR = 0.0325 with 63 structural parameters. The structure of the first subsystem is the alternate stacking of an edge-shared InO(6) octahedral layer and an Fe/Ti triangle-lattice plane along c. A sheet of O atoms in the second subsystem is also extending on the Fe/Ti plane, where displacive modulation of atoms is prominent.

Crystal structure and charge distribution of YbFeMnO4.

The structure of synthetic YbFeMnO(4) has been refined by single-crystal X-ray diffraction. Space group R3m, a = 3.4580 (1), c = 25.647 (3) A, V = 265.59 (3) A(3), Z = 3. Yb is in octahedral coordination, whereas Fe and Mn are disordered on a single crystallographic type of trigonal bipyramid, in which the cation is off-centred from the basal plane. Assuming perfect stoichiometry, R(1) = 0.0195, but the charge distribution (CD) analysis suggests incomplete occupation of the Yb site. Refinement of the occupancy lowers R(1) to 0.0175, resulting in s.o.f.(Yb) = 0. 963 (3), with a significant improvement of the Fourier difference. The electroneutrality is likely preserved through incomplete occupancy of one of the two oxygen sites: the compound is thus non-stoichiometric, with the formula Yb(0.963)FeMnO(3.945). Another mechanism for preserving the electroneutrality is the oxidation of a small amount of Mn(2+) to Mn(3+), which is, however, less probable because of the reduction conditions in which the sample was synthesized. Both models give a satisfactorily CD result, but they cannot be definitively distinguished by X-ray data.

Relation between In ion ordering and crystal structure variation in homologous compounds InMO3(ZnO)m (M = Al and In; m = integer)

The relation between the ordering of In ions and the structure variation of homologous compounds InInO3(ZnO)13 and InAlO3(ZnO)m (m = 4, 5, and 13) have been studied by high-resolution transmission electron microscopy. It is revealed that InMO3(ZnO)m is a layered structure, consisting of InO2(1-) (In-O) and MZn(m)Om+1(1+) (M/Zn-O) layers stacked alternatively. Structure variations from the basic one, caused by the ordering of In ions in the M/Zn-O layers, are observed both in In2O3(ZnO)m and InAlO3(ZnO)m. In In2O3(ZnO)m, a modulated structure appearing as zig-zag shaped contrast in the high-resolution image was found and is considered to be caused by the ordering of In ions along the zig-zag contrast area. In InAlO3(ZnO)m, no modulated structure was found. Instead, planar defect structures appearing in Al/Zn-O layers were observed. It is shown that this defect structure is caused by the excess introduction of In ions into the Al/Zn-O layers and the ordering of these In ions. By comparing the results of InInO3(ZnO)m and InAlO3(ZnO)m, it is shown that the reasons for the In ion ordering is the discrepancy between the larger In ion size and the smaller oxygen void for M/Zn ions in M/Zn-O layers.

Molecular Dispersion of Chains in the Mixed-Valence Complexes

A way to prepare molecular electronic wires in organic media is the solubilization of one-dimensional mixed-valence complexes with varied metal species through the formation of amphiphilic supramolecular assemblies (see picture). Dissociation and reassembly of the complex was detected as thermochromism in the intervalence (M(II)-->M(IV)) absorption bands.

Self-assembling molecular wires of halogen-bridged platinum complexes in organic media. Mesoscopic supramolecular assemblies consisting of a mixed valent Pt(II)/Pt(IV) complex and anionic amphiphiles.

A novel class of supramolecular assemblies in organic media consisting of a molecular wire of a halogen-bridged platinum complex [Pt(en)2][PtCl2(en)2]4+ (en = 1,2-diaminoethane) and anionic amphiphiles is developed. When double-chained phosphates or sulfonates are employed, the resultant [Pt(en)2][PtCl2(en)2](4+)-lipid complexes displayed intervalence charge transfer (CT) absorption bands in the crystalline state. They are soluble in organic solvents because of the amphiphilic superstructure, in which the solvophobic one-dimensional platinum complex is surrounded by solvophilic alkyl chains. CT absorption bands of halogen-bridged linear complexes are maintained in organic media, with varied colors that depend on the chemical structure of constituent amphiphiles. Monoalkylated phosphates failed to form colored, halogen-bridged ternary complexes probably because of their coordination to the axial position of PtII(en)2. Formation of mesoscopic supramolecular assemblies in organic media was confirmed for the [Pt(en)2][PtCl2(en)2] complexes by electron microscopy. Interestingly, a supramolecular complex consisting of dihexadecyl sulfosuccinate and [Pt(en)2][PtCl2(en)2]4+ displayed clear, indigo solutions that are distinct from the yellow color observed for those of [Pt(en)2][PtCl2(en)2]/dialkyl phosphate complexes. The indigo color of the former complex disappeared upon heating the solution to 60 degrees C, whereas it reappeared reversibly by cooling the solution to room temperature. In electron microscopy, rodlike nanostructures with a minimum width of 18 nm and lengths of 700-1700 nm were observed after cooling, though not at elevated temperatures. Apparently, the lipid-[Pt(en)2][PtCl2(en)2]4+ complex undergoes reversible dissociation and reassembly processes in chloroform, and it becomes better dispersed after the reassembling process. The present finding opens a general route to solution chemistry of low-dimensional inorganic complexes and enables rational design and control of self-assembling inorganic molecular wires.

Structure analysis of new homologous compounds Ga2O3(ZnO)m (m = integer) by high-resolution analytical transmission electron microscopy.

The crystal structure of a new homologous compound series, Ga(2)O(3)(ZnO)(m) (m = integer), is determined by high-resolution lattice imaging and high spatial resolution energy-dispersive X-ray spectroscopy (EDS) analysis in a field-emission analytical transmission electron microscope. This work was carried out mainly on the compound with m = 9 (digallium nonazinc dodecaoxide), which belongs to the orthorhombic system and has lattice constants a(o) = 0.33, b(o) = 2.0 and c(o) = 3.4 nm. From the extinction rules three possible space groups are selected and from them a unique space group is assigned as noncentrosymmetric Cmc2(1) (No. 36) on the basis of structural requirements. Ga(2)O(3)(ZnO)(m) is a layered structure consisting of Ga-O and m + 1 Ga/Zn-O layers stacked alternately along the c axis. It is shown that the structure of Ga(2)O(3)(ZnO)(m) differs from that of M(2)O(3)(ZnO)(m) (M = In, Fe; m = integer) reported previously. In Ga(2)O(3)(ZnO)(m) the Ga atoms occupy the tetrahedral sites in the Ga-O layers, whereas the M atoms in the M-O layers occupy the octahedral sites in M(2)O(3)(ZnO)(m) (M = In, Fe).