RESUMEN
Metal-organic frameworks (MOFs) have emerged as promising tailor-designed materials for developing next-generation solid-state devices with applications in linear and nonlinear coherent optics. However, the implementation of functional devices is challenged by the notoriously difficult process of growing large MOF single crystals of high optical quality. By controlling the solvothermal synthesis conditions, we succeeded in producing large individual single crystals of the noncentrosymmetric MOF Zn(3-ptz)2 (MIRO-101) with a deformed octahedron habit and surface areas of up to 37 mm2. We measured the UV-vis absorption spectrum of individual Zn(3-ptz)2 single crystals across different lateral incidence planes. Millimeter-sized single crystals have a band gap of E g = 3.32 eV and exhibit anisotropic absorption in the band-edge region near 350 nm, whereas polycrystalline samples are fully transparent in the same frequency range. Using solid-state density functional theory (DFT), the observed size dependence in the optical anisotropy is correlated with the preferred orientation adopted by pyridyl groups under conditions of slow crystal self-assembly. Our work thus paves the way for the development of optical polarization switches based on metal-organic frameworks.
RESUMEN
The solvothermal synthesis of metal-organic frameworks (MOFs) often proceeds through competing crystallization pathways, and only partial control over the crystal nucleation and growth rates is possible. It challenges the use of MOFs as functional devices in free-space optics, where bulk single crystals of millimeter dimensions and high optical quality are needed. We develop a synthetic protocol to control the solvothermal growth of the MOF [Zn(3-ptz)2] n (MIRO-101), to obtain large single crystals with projected surface areas of up to 25 mm2 in 24 h, in a single reaction with in situ ligand formation. No additional cooling and growth steps are necessary. We propose a viable reaction mechanism for the formation of MIRO-101 crystals under acidic conditions, by isolating intermediate crystal structures that directly connect with the target MOF and reversibly interconverting between them. We also study the nucleation and growth kinetics of MIRO-101 using ex situ crystal image analysis. The synthesis parameters that control the size and morphology of our target MOF crystal are discussed. Our work deepens our understanding of MOF growth processes in solution and demonstrates the possibility of building MOF-based devices for future applications in optics.
RESUMEN
We describe the structure and properties of [Zn(C6H4N5)N3] n , a new nonporous three-dimensional high-energy metal-organic framework (HE-MOF) with enhanced thermal stability. The compound is synthesized by the hydrothermal method with in situ ligand formation under controlled pH and characterized using single-crystal X-ray diffraction, elemental analysis, and Fourier transform infrared. The measured detonation temperature (T det = 345 °C) and heat of detonation (ΔH det = -0.380 kcal/g) compare well with commercial explosives and other nitrogen-rich HE-MOFs. The velocity and pressure of denotation are 5.96 km/s and 9.56 GPa, respectively. Differential scanning calorimetry analysis shows that the denotation of [Zn(C6H4N5)N3] n occurs via a complex temperature-dependent mechanism.
RESUMEN
The title compound, [Ni(C10H8N2)3](C9H5N4O)2·2H2O, crystallizes as a racemic mixture in the monoclinic space group C2/c. In the crystal, the 1,1,3,3-tetracyano-2-ethoxypropenide anions and the water molecules are linked by O-Hâ¯N hydrogen bonds, forming chains running along the [010] direction. The bpy ligands of the cation are linked to the chain via C-Hâ¯π(cation) inter-actions involving the CH3 group. The inter-molecular inter-actions were investigated by Hirshfeld surface analysis and two-dimensional fingerprint plots.
RESUMEN
Hexa-aqua-zinc(II) dinitrate 5-(pyridinium-3-yl)tetra-zol-1-ide, [Zn(H2O)6](NO3)2·2C6H5N5, crystallizes in the space group P . The asymmetric unit contains one zwitterionic 5-(pyridinium-3-yl)tetra-zol-1-ide mol-ecule, one NO3- anion and one half of a [Zn(H2O)6]2+ cation ( symmetry). The pyridinium and tetra-zolide rings in the zwitterion are nearly coplanar, with a dihedral angle of 5.4â (2)°. Several O-Hâ¯N and N-Hâ¯O hydrogen-bonding inter-actions exist between the [Zn(H2O)6]2+ cation and the N atoms of the tetra-zolide ring, and between the nitrate anions and the N-H groups of the pyridinium ring, respectively, giving rise to a three-dimensional network. The 5-(pyridinium-3-yl)tetra-zol-1-ide mol-ecules show parallel-displaced π-π stacking inter-actions; the centroid-centroid distance between adjacent tetra-zolide rings is 3.6298â (6)â Å and that between the pyridinium and tetra-zolide rings is 3.6120â (5)â Å.
RESUMEN
We report the synthesis and structural diversity of Zn(II) metal-organic framework (MOF) with in situ formation of tetrazole ligand 3-ptz [3-ptz = 5-(3-pyridyl)tetrazolate] as a function pH. By varying the initial reaction pH, we obtain high-quality crystals of the noncentrosymmetric three-dimensional MOF Zn(3-ptz)2 , mixed phases involving the zinc-aqua complex [Zn(H2O)4(3-ptz)2]·4H2O, and two-dimensional MOF crystals Zn(OH)(3-ptz) with a tunable microrod morphology, keeping reaction time, temperature, and metal-ligand molar ratio constant. Structures are characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis spectroscopy. We discuss the observed structural diversity in terms of the relative abundance of hydroxo-zinc species in solution for different values of pH.