Upconverted excitonic photoluminescence from a two-dimensional lead-halide perovskite.

Anti-Stokes photoluminescence (AS-PL) is an interesting optical phenomenon that can cause laser cooling in certain semiconductors where incident laser photons are efficiently converted into photons with higher energy. The underlying upconversion mechanism can be used to realize optical refrigerators, but suited materials need to be developed for actual applications. Here, we investigate the AS-PL properties of a two-dimensional (2D) perovskite PEA2PbI4 single crystal and compare them with those of a three-dimensional (3D) perovskite MAPbI3 single crystal. We find that, in the 2D perovskite PEA2PbI4, which has a large exciton binding energy, the free-exciton PL is dominant and that the measured upconversion gain spectra of both PEA2PbI4 and MAPbI3 crystals are similar. The AS-PL process in these perovskite single crystals is discussed.

Large negative thermo-optic coefficients of a lead halide perovskite.

Lead halide perovskites are promising semiconductors for high-performance photonic devices. Because the refractive index determines the optimal design and performance limit of the semiconductor devices, the refractive index and its change upon external modulations are the most critical properties for advanced photonic applications. Here, we report that the refractive index of halide perovskite CH3NH3PbCl3 shows a distinct decrease with increasing temperature, i.e., a large negative thermo-optic coefficient, which is opposite to those of conventional inorganic semiconductors. By using this negative coefficient, we demonstrate the compensation of thermally induced optical phase shifts occurring in conventional semiconductors. Furthermore, we observe a large and slow refractive index change in CH3NH3PbCl3 during photoirradiation and clarify its origin to be a very low thermal conductivity supported by theoretical analysis. The giant thermo-optic response of CH3NH3PbCl3 facilitates efficient phase modulation of visible light.

Longitudinal Optical Phonons Modified by Organic Molecular Cation Motions in Organic-Inorganic Hybrid Perovskites.

We performed terahertz time-domain spectroscopy for methylammonium (MA) lead halide perovskite single crystals and characterized the longitudinal optical (LO) phonons directly. We found that the effective LO phonon wave number does not change in the wide temperature range between 10 and 300 K. However, the coupling between MA cation modes and the LO phonon mode derived from lead halide cages induces a mode splitting at low temperatures and a damping of the LO phonon mode at high temperatures. These results influence the interpretation of electron-LO phonon interactions in perovskite semiconductors, as well as the interpretations of mobility, carrier diffusion, and polaron formation.

Near-Band-Edge Optical Responses of CH_{3}NH_{3}PbCl_{3} Single Crystals: Photon Recycling of Excitonic Luminescence.

The determination of the band gap and exciton energies of lead halide perovskites is very important from the viewpoint of fundamental physics and photonic device applications. By using photoluminescence excitation (PLE) spectra, we reveal the optical properties of CH_{3}NH_{3}PbCl_{3} single crystals in the near-band-edge energy regime. The one-photon PLE spectrum exhibits the 1s exciton peak at 3.11 eV. On the contrary, the two-photon PLE spectrum exhibits no peak structure. This indicates photon recycling of excitonic luminescence. By analyzing the spatial distribution of the excitons and photon recycling, we obtain 3.15 eV for the band gap energy and 41 meV for the exciton binding energy.

A Stable, Soluble, and Crystalline Supramolecular System with a Triplet Ground State.

A supramolecular complex was constructed by encapsulation of a 3 O2 molecule inside an open-cage C60 derivative. Its single-crystal X-ray diffraction analysis revealed the presence of the 3 O2 at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated 3 O2 after two-electron reduction. The ESR measurements displayed the triplet character as well as the anisotropy of the 3 O2 . Additionally, the SQUID measurements also demonstrated the paramagnetic behavior above 3 K without an antiferromagnetic transition. Upon photoirradiation with visible light, three phosphorescent bands at the NIR region were observed, arising from the exited 1 O2 generated by self-sensitization with the outer cage, whose lifetimes were not affected by the environments. These studies confirmed that the complex is a crystalline triplet system with incompatible "high spin density" but "small interspin interaction" properties.

From Tetrahedral to Octahedral Iron Coordination: Layer Compression in Topochemically Prepared FeLa2Ti3O10.

Synthesis, characterization, and thermal modification of the new layered perovskite FeLa2Ti3O10 have been studied. FeLa2Ti3O10 was prepared by ion exchange of the triple-layered Ruddlesden-Popper phase Li2La2Ti3O10 with FeCl2 at 350 °C under static vacuum. Rietveld refinement on synchrotron X-ray diffraction data indicates that the new phase is isostructural with CoLa2Ti3O10, where FeII cations occupy slightly compressed/flattened interlayer tetrahedral sites. Magnetic measurements on FeLa2Ti3O10 display Curie-Weiss behavior at high temperatures and a spin-glass transition at lower temperatures (<30 K). Thermal treatment in oxygen shows that FeLa2Ti3O10 undergoes a significant cell contraction (Δc ≈ -2.7 Å) with a change in the oxidation state of iron (Fe2+ to Fe3+); structural analysis and Mössbauer studies indicate that upon oxidation the local iron environment goes from tetrahedral to octahedral coordination with some deintercalation of iron as Fe2O3 to produce Fe0.67La2Ti3O10.

Optical characterization of voltage-accelerated degradation in CH3NH3PbI3 perovskite solar cells.

We investigate the performance degradation mechanism of CH3NH3PbI3 perovskite solar cells under bias voltage in air and nitrogen atmospheres using photoluminescence and electroluminescence techniques. When applying forward bias, the power conversion efficiency of the solar cells decreased significantly in air, but showed no degradation in nitrogen atmosphere. Time-resolved photoluminescence measurements on these devices revealed that the application of forward bias in air accelerates the generation of non-radiative recombination centers in the perovskite layer buried in the device. We found a negative correlation between the electroluminescence intensity and the injected current intensity in air. The irreversible change of the perovskite grain surface in air initiates the degradation of the perovskite solar cells.

Synthesis of a distinct water dimer inside fullerene C70.

The water dimer is an ideal chemical species with which to study hydrogen bonds. Owing to the equilibrium between the monomer and oligomer structure, however, selective generation and separation of a genuine water dimer has not yet been achieved. Here, we report a synthetic strategy that leads to the successful encapsulation of one or two water molecules inside fullerene C70. These endohedral C70 compounds offer the opportunity to study the intrinsic properties of a single water molecule without any hydrogen bonding, as well as an isolated water dimer with a single hydrogen bond between the two molecules. The unambiguously determined off-centre position of water in (H2O)2@C70 by X-ray diffraction provides insights into the formation of (H2O)2@C70. Subsequently, the (1)H NMR spectroscopic measurements for (H2O)2@C70 confirmed the formation of a single hydrogen bond rapidly interchanging between the encapsulated water dimer. Our theoretical calculations revealed a peculiar cis-linear conformation of the dimer resulting from confinement effects inside C70.

Topochemical Nitridation with Anion Vacancy-Assisted N(3-)/O(2-) Exchange.

We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x ∼ 0.18). At 400 °C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi(3.82+)O2.82H0.18, leading to the N(3-)/H(-)-exchanged product EuTi(4+)O2.82N0.12□0.06. When the ammonolysis temperature was increased up to 800 °C, we observed a further nitridation involving N(3-)/O(2-) exchange, yielding a fully oxidized Eu(3+)Ti(4+)O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N(3-) with O(2-) only above 600 °C and resulted in incomplete nitridation to EuTiO2.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N(3-)/O(2-)) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.

An unprecedented Co(II) cuboctahedron as the secondary building unit in a Co-based metal-organic framework.

A cubic metal-organic framework with an unprecedented octanuclear secondary building unit (SBU) was isolated. The obtained SBU is composed of 8 Co(II) ions at each vertex, 6 µ4-OH groups at each face, and 12 cpt(-) ligands framing the metal core. The cuboctahedra arrange in a ubt framework topology, eliciting a highly symmetrical MOF structure. Magnetic measurements as well as DFT calculations on this crystalline MOF reveal intramolecular antiferromagnetic coupling between Co(II) ions in the octanuclear SBU.

Novel Co-based metal-organic frameworks and their magnetic properties using asymmetrically binding 4-(4'-carboxyphenyl)-1,2,4-triazole.

Two novel Co-based metal-organic frameworks (MOFs) were synthesised and characterised using an asymmetrically binding ligand, 4-(4'-carboxyphenyl)-1,2,4 triazole (Hcpt). The isolated [Co3(II)(µ3-O)(OH)(cpt)3(H2O)2]n·xH2O·yDMF, Co-MOF1, exhibits a rhombohedral crystal structure (space group, P63/mc), with a trinuclear cobalt core that resembles the MIL88 series. This MOF shows paramagnetic behaviour down to 2 K with no saturation of magnetisation up to 7 T. This is presumably due to a geometrically frustrated triangular arrangement of Co spins. The two-dimensional complex, [Co(II)(cpt)(N3)]n, Co-MOF2, crystallises in a monoclinic crystal system (space group, C2/m). The magnetic measurements reveal metamagnetic behaviour for this complex with a critical field in the range of 700-1000 Oe.

High-temperature spin crossover behavior in a nitrogen-rich Fe(III)-based system.

A nitrogen-rich ligand bis(1H-tetrazol-5-yl)amine (H(3)bta) was employed to isolate a new Fe(III) complex, Na(2)NH(4)[Fe(III)(Hbta)(3)]·3DMF·2H(2)O (1). Single crystal X-ray diffraction revealed that complex 1 consists of Fe(III) ions in an octahedral environment where each metal ion is coordinated by three Hbta(2-) ligands forming the [Fe(III)(Hbta)(3)](3-) core. Each unit is linked to two one-dimensional (1-D) Na(+)/solvent chains creating a two-dimensional (2-D) network. In addition, the presence of multiple hydrogen bonds in all directions between ammonium cation and ligands of different [Fe(III)(Hbta)(3)](3-) units generates a three-dimensional (3-D) network. Magnetic measurements confirmed that the Fe(III) center undergoes a Spin Crossover (SCO) at high temperature (T(1/2) = 460(10) K).

Paramagnetic Nanocrystals: Remarkable Lanthanide-Doped Nanoparticles with Varied Shape, Size, and Composition.

Magnetic nanoparticles have been developed in recent years with applications in unique and crucial areas such as biomedicine, data storage, environmental remediation, catalysis, and so forth. NaYF4 nanoparticles were synthesized and isolated with lanthanide dopant percentages, confirmed by ICP-OES measurements, of Er, Yb, Tb, Gd, and Dy that were in agreement with the targeted ratios. SEM images showed a distinct variation in particle size and shape with dopant type and percentage. HRTEM and XRD studies confirmed the particles to be crystalline, possessing both α and ß phases. Magnetic measurements determined that all of the nanoparticles were paramagnetic and did not exhibit a blocking temperature from 2 to 300 K. The multifunctional properties of these nanoparticles make them suitable for many applications, such as multimodal imaging probes, up-conversion fluorescent markers, as well as MRI contrast agents.

Planar tetranuclear Dy(III) single-molecule magnet and its Sm(III), Gd(III), and Tb(III) analogues encapsulated by salen-type and ß-diketonate ligands.

The syntheses, structures, and magnetic properties are reported for four new lanthanide clusters [Sm(4)(µ(3)-OH)(2)L(2)(acac)(6)]·4H(2)O (1), [Gd(4)(µ(3)-OH)(2)L(2)(acac)(6)]·4CH(3)CN (2), and [Ln(4)(µ(3)-OH)(2)L(2)(acac)(6)]·2H(2)L·2CH(3)CN (3, Ln = Tb; 4, Ln = Dy) supported by salen-type (H(2)L = N,N'-bis(salicylidene)-1,2-cyclohexanediamine) and ß-diketonate (acac = acetylacetonate) ligands. The four clusters were confirmed to be essentially isomorphous by infrared spectroscopy and single-crystal X-ray diffraction. Their crystal structures reveal that the salen-type ligand provides a suitable tetradentate coordination pocket (N(2)O(2)) to encapsulate lanthanide(III) ions. Moreover, the planar Ln(4) core is bridged by two µ(3)-hydroxide, four phenoxide, and two ketonate oxygen atoms. Magnetic properties of all four compounds have been investigated using dc and ac susceptibility measurements. For 4, the static and dynamic data indicate that the Dy(4) complex exhibits slow relaxation of the magnetization below 5 K associated with single-molecule magnet behavior.