Oriented Growth of In-Oxo Chain Based Metal-Porphyrin Framework Thin Film for High-Sensitive Photodetector

The potential of metal–organic frameworks (MOFs) for applications in optoelectronics results from a unique combination of interesting photophysical properties and straightforward tunability of organic and inorganic units. Here, it is demonstrated that using MOF approach chromophores can be assembled into well-ordered 1D arrays using metal-oxo strands as lead structure, and the resulting porphyrinic rows exhibit unique photophysical properties and allow the realization of highly sensitive photodetectors. A porphyrinic MOF thin film, In-TCPP surface-coordinated MOF thin films with [021] orientation is fabricated using a layer-by-layer method, from In(NO$_{3}$)$_{3}$ and TCPP (5,10,15,20-(4-carboxyphenyl)porphyrin). Detailed experimental and theoretical analysis reveals that the assembly yields a structure where In-oxo strands running parallel to the substrate fix the chromophoric linkers to yield 1D arrays of porphyrins. The frontier orbitals of this highly anisotropic arrangement are localized in these columnar arrangements of porphyrins and result in high photoactivity, which is exploited to fabricate a photodetector with record (as compared to other organic materials) responsivity in visible regime of 7.28 × 10$^{14}$ Jones and short rise/fall times (0.07/0.04 s). This oriented MOF thin film-based high-sensitive photodetector provides a new avenue to use inorganic, stable lead structures to assemble organic semiconductors into regular arrays, thus creating a huge potential for the fabrication of optoelectronic devices

Data publication: Strong Binding of Noble Gases to [B₁₂X₁₁]⁻: a theoretical study

This dataset contains output files of DFT and DLPNO calculations of the investigated species. At the DFT level of theory full geometry optimizations and frequency analysis where done. At DLPNO level of theory single point calculations were done

Strong Binding of Noble Gases to [B12X11]˗: A Theoretical Study

We systematically explore the stability and properties of [B12X11Ng]− adducts resulting from the capture reaction of noble gas atoms (Ng) by anionic [B12X11]− clusters in the ion trap. [B12X11]− can be obtained by stripping one X− ligand off the icosahedral closo-dodecaborate dianion [B12X12]2−. We study the binding of the noble gas atoms He, Ne, Kr, Ar and Xe to [B12X11]− with ligands X = F, Cl, Br, I, CN. While He cannot be captured by these clusters and Ne only binds at low temperatures, the complexes with the heavier Kr, Ar and Xe show appreciable complexation energies and exceed 1 eV at room temperature in the case of [B12(CN)11Xe]−. For the latter three noble gases, we observe a significant charge transfer from the Ng to the icosahedral B12 cage

The polyoxo-22-palladate( ii ), [Na2_{2} PdII^{II}22_{22}O12_{12} (AsV^{V}O4_{4} )15_{15} (AsV^{V}O3_{3}OH)]25−^{25−}

The polyoxo-22-palladate [Na2PdII22O12(AsVO4)15(AsVO3OH)]25− (1), which represents a novel polyoxo-noble-metalate structural type, was synthesized by reaction of Pd2+ and AsO43− ions in aqueous solution.</p

Oriented Growth of In‐Oxo Chain Based Metal‐Porphyrin Framework Thin Film for High‐Sensitive Photodetector

The potential of metal–organic frameworks (MOFs) for applications in optoelectronics results from a unique combination of interesting photophysical properties and straightforward tunability of organic and inorganic units. Here, it is demonstrated that using MOF approach chromophores can be assembled into well‐ordered 1D arrays using metal‐oxo strands as lead structure, and the resulting porphyrinic rows exhibit unique photophysical properties and allow the realization of highly sensitive photodetectors. A porphyrinic MOF thin film, In‐TCPP surface‐coordinated MOF thin films with [021] orientation is fabricated using a layer‐by‐layer method, from In(NO(3))(3) and TCPP (5,10,15,20‐(4‐carboxyphenyl)porphyrin). Detailed experimental and theoretical analysis reveals that the assembly yields a structure where In‐oxo strands running parallel to the substrate fix the chromophoric linkers to yield 1D arrays of porphyrins. The frontier orbitals of this highly anisotropic arrangement are localized in these columnar arrangements of porphyrins and result in high photoactivity, which is exploited to fabricate a photodetector with record (as compared to other organic materials) responsivity in visible regime of 7.28 × 10(14) Jones and short rise/fall times (0.07/0.04 s). This oriented MOF thin film‐based high‐sensitive photodetector provides a new avenue to use inorganic, stable lead structures to assemble organic semiconductors into regular arrays, thus creating a huge potential for the fabrication of optoelectronic devices

Chemical Speciation of Metal Complexes from Chemical Shift Calculations: The Interaction of 2‑Amino‑<i>N</i>‑hydroxypropanamide with V(V) in Aqueous Solution

The chemical speciation of 2-amino-<i>N</i>-hydroxypropanamide (β-alaninohydroxamic acid, HL) and vanadium (V) in aqueous solution has been investigated through calculations of the thermodynamic properties and the ⁵¹V nuclear magnetic resonance (NMR) chemical shifts of the species formed at equilibrium. The results have been compared directly with the experimental ⁵¹V NMR data. The ⁵¹V NMR chemical shifts have been calculated by using a density functional theory (DFT) approach accounting for relativistic corrections and solvent effects. All tautomers of the 1:1 and 1:2 VO₂⁺/β-ala complexes with different degrees of protonation have been calculated and thermodynamic and structural properties are presented for the most stable species. The system is better modeled as tautomeric equilibria, and species lying down in the range of 10 kcal·mol^–1 cannot be neglected at the BP/TZ2P/COSMO approach. In fact, the metal complex speciation in aqueous solution should not be investigated based solely on the thermodynamic analysis, but together with spectroscopic calculations such as NMR

From icosahedron to a plane flattening dodecaiodo-dodecaborate by successive stripping of iodine

It has been shown by electrospray ionization–ion-trap mass spectrometry that B12I122− converts to an intact B12 cluster as a result of successive stripping of single iodine radicals or ions. Herein, the structure and stability of all intermediate B12In− species (n=11 to 1) determined by means of first-principles calculations are reported. The initial predominant loss of an iodine radical occurs most probably via the triplet state of B12I122−, and the reaction path for loss of an iodide ion from the singlet state crosses that from the triplet state. Experimentally, the boron clusters resulting from B12I122− through loss of either iodide or iodine occur at the same excitation energy in the ion trap. It is shown that the icosahedral B12 unit commonly observed in dodecaborate compounds is destabilized while losing iodine. The boron framework opens to nonicosahedral structures with five to seven iodine atoms left. The temperature of the ions has a considerable influence on the relative stability near the opening of the clusters. The most stable structures with five to seven iodine atoms are neither planar nor icosahedral.Spanish Ministerio de Ciencia e Innovación (CTQ2010–16237), CSIC (I3P grant to P.F.), the Generalitat de Catalunya (2009/SGR/00279), and the Center for Functional Nanomaterials (NanoFun) of Jacobs University Bremen.peer-reviewe