Cova de Can Sadurní, la transformació d’un jaciment. L’episodi sepulcral del neolític postcardial

The present study deals with the structural characterization and classification of the novel compounds <b>1</b>–<b>8</b> into perovskite subclasses and proceeds in extracting the structure–band gap relationships between them. The compounds were obtained from the employment of small, 3–5-atom-wide organic ammonium ions seeking to discover new perovskite-like compounds. The compounds reported here adopt unique or rare structure types akin to the prototype structure perovskite. When trimethylammonium (TMA) was employed, we obtained TMASnI₃ (<b>1</b>), which is our reference compound for a “perovskitoid” structure of face-sharing octahedra. The compounds EASnI₃ (<b>2b</b>), GASnI₃ (<b>3a</b>), ACASnI₃ (<b>4</b>), and IMSnI₃ (<b>5</b>) obtained from the use of ethylammonium (EA), guanidinium (GA), acetamidinium (ACA), and imidazolium (IM) cations, respectively, represent the first entries of the so-called “hexagonal perovskite polytypes” in the hybrid halide perovskite library. The hexagonal perovskites define a new family of hybrid halide perovskites with a crystal structure that emerges from a blend of corner- and face-sharing octahedral connections in various proportions. The small organic cations can also stabilize a second structural type characterized by a crystal lattice with reduced dimensionality. These compounds include the two-dimensional (2D) perovskites GA₂SnI₄ (<b>3b</b>) and IPA₃Sn₂I₇ (<b>6b</b>) and the one-dimensional (1D) perovskite IPA₃SnI₅ (<b>6a</b>). The known 2D perovskite BA₂MASn₂I₇ (<b>7</b>) and the related all-inorganic 1D perovskite “RbSnF₂I” (<b>8</b>) have also been synthesized. All compounds have been identified as medium-to-wide-band-gap semiconductors in the range of <i>E</i>_g = 1.90–2.40 eV, with the band gap progressively decreasing with increased corner-sharing functionality and increased torsion angle in the octahedral connectivity

CO Binding at a Four-Coordinate Cobaltous Porphyrin Site in a Metal–Organic Framework: Structural, EPR, and Gas Adsorption Analysis

The variable-temperature CO binding at a four-coordinate cobaltous porphyrin complex within a metal–organic framework is investigated using a combined array of infrared, X-ray diffraction, EPR, and CO adsorption analysis. Single-crystal X-ray diffraction experiments provide the first crystallographically characterized example of a noniron first-row transition metal porphyrin carbonyl adduct. Variable-temperature electron paramagnetic resonance spectroscopy supports the structural observation and reveals conversion of the dicarbonyl complex to a monocarbonyl species as temperature is increased. Finally, CO adsorption analysis data enable quantification of the Co–CO interaction, providing a binding enthalpy of <i>h</i>_ads = −29(2) kJ/mol. This value is nearly twice that observed for O₂ binding in the same compound and is attributed to a stronger σ interaction for Co and CO vs O₂. These results demonstrate the ability of MOFs to enable a thorough investigation of CO binding in metalloporphyrins

CO Binding at a Four-Coordinate Cobaltous Porphyrin Site in a Metal–Organic Framework: Structural, EPR, and Gas Adsorption Analysis

The variable-temperature CO binding at a four-coordinate cobaltous porphyrin complex within a metal–organic framework is investigated using a combined array of infrared, X-ray diffraction, EPR, and CO adsorption analysis. Single-crystal X-ray diffraction experiments provide the first crystallographically characterized example of a noniron first-row transition metal porphyrin carbonyl adduct. Variable-temperature electron paramagnetic resonance spectroscopy supports the structural observation and reveals conversion of the dicarbonyl complex to a monocarbonyl species as temperature is increased. Finally, CO adsorption analysis data enable quantification of the Co–CO interaction, providing a binding enthalpy of <i>h</i>_ads = −29(2) kJ/mol. This value is nearly twice that observed for O₂ binding in the same compound and is attributed to a stronger σ interaction for Co and CO vs O₂. These results demonstrate the ability of MOFs to enable a thorough investigation of CO binding in metalloporphyrins

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties

A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI₃, where A is the methylammonium (CH₃NH₃⁺) or formamidinium (HC­(NH₂)₂⁺) cation and M is Sn (<b>1</b> and <b>2</b>) or Pb (<b>3</b> and <b>4</b>) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of <b>1</b>–<b>4</b> classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that <b>1</b>–<b>4</b> behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25–1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700–1000 nm range (1.1–1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range. The optical properties such as energy band gap, emission intensity, and wavelength can be readily controlled as we show for the isostructural series of solid solutions CH₃NH₃Sn_1–<i>x</i>Pb_<i>x</i>I₃ (<b>5</b>). The charge transport type in these materials was characterized by Seebeck coefficient and Hall-effect measurements. The compounds behave as <i>p</i>- or <i>n</i>-type semiconductors depending on the preparation method. The samples with the lowest carrier concentration are prepared from solution and are <i>n</i>-type; <i>p</i>-type samples can be obtained through solid state reactions exposed in air in a controllable manner. In the case of Sn compounds, there is a facile tendency toward oxidation which causes the materials to be doped with Sn⁴⁺ and thus behave as <i>p</i>-type semiconductors displaying metal-like conductivity. The compounds appear to possess very high estimated electron and hole mobilities that exceed 2000 cm²/(V s) and 300 cm²/(V s), respectively, as shown in the case of CH₃NH₃SnI₃ (<b>1</b>). We also compare the properties of the title hybrid materials with those of the “all-inorganic” CsSnI₃ and CsPbI₃ prepared using identical synthetic methods

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties

A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI₃, where A is the methylammonium (CH₃NH₃⁺) or formamidinium (HC­(NH₂)₂⁺) cation and M is Sn (<b>1</b> and <b>2</b>) or Pb (<b>3</b> and <b>4</b>) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of <b>1</b>–<b>4</b> classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that <b>1</b>–<b>4</b> behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25–1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700–1000 nm range (1.1–1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range. The optical properties such as energy band gap, emission intensity, and wavelength can be readily controlled as we show for the isostructural series of solid solutions CH₃NH₃Sn_1–<i>x</i>Pb_<i>x</i>I₃ (<b>5</b>). The charge transport type in these materials was characterized by Seebeck coefficient and Hall-effect measurements. The compounds behave as <i>p</i>- or <i>n</i>-type semiconductors depending on the preparation method. The samples with the lowest carrier concentration are prepared from solution and are <i>n</i>-type; <i>p</i>-type samples can be obtained through solid state reactions exposed in air in a controllable manner. In the case of Sn compounds, there is a facile tendency toward oxidation which causes the materials to be doped with Sn⁴⁺ and thus behave as <i>p</i>-type semiconductors displaying metal-like conductivity. The compounds appear to possess very high estimated electron and hole mobilities that exceed 2000 cm²/(V s) and 300 cm²/(V s), respectively, as shown in the case of CH₃NH₃SnI₃ (<b>1</b>). We also compare the properties of the title hybrid materials with those of the “all-inorganic” CsSnI₃ and CsPbI₃ prepared using identical synthetic methods

CO Binding at a Four-Coordinate Cobaltous Porphyrin Site in a Metal–Organic Framework: Structural, EPR, and Gas Adsorption Analysis

The variable-temperature CO binding at a four-coordinate cobaltous porphyrin complex within a metal–organic framework is investigated using a combined array of infrared, X-ray diffraction, EPR, and CO adsorption analysis. Single-crystal X-ray diffraction experiments provide the first crystallographically characterized example of a noniron first-row transition metal porphyrin carbonyl adduct. Variable-temperature electron paramagnetic resonance spectroscopy supports the structural observation and reveals conversion of the dicarbonyl complex to a monocarbonyl species as temperature is increased. Finally, CO adsorption analysis data enable quantification of the Co–CO interaction, providing a binding enthalpy of <i>h</i>_ads = −29(2) kJ/mol. This value is nearly twice that observed for O₂ binding in the same compound and is attributed to a stronger σ interaction for Co and CO vs O₂. These results demonstrate the ability of MOFs to enable a thorough investigation of CO binding in metalloporphyrins

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties

A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI₃, where A is the methylammonium (CH₃NH₃⁺) or formamidinium (HC­(NH₂)₂⁺) cation and M is Sn (<b>1</b> and <b>2</b>) or Pb (<b>3</b> and <b>4</b>) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of <b>1</b>–<b>4</b> classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that <b>1</b>–<b>4</b> behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25–1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700–1000 nm range (1.1–1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range. The optical properties such as energy band gap, emission intensity, and wavelength can be readily controlled as we show for the isostructural series of solid solutions CH₃NH₃Sn_1–<i>x</i>Pb_<i>x</i>I₃ (<b>5</b>). The charge transport type in these materials was characterized by Seebeck coefficient and Hall-effect measurements. The compounds behave as <i>p</i>- or <i>n</i>-type semiconductors depending on the preparation method. The samples with the lowest carrier concentration are prepared from solution and are <i>n</i>-type; <i>p</i>-type samples can be obtained through solid state reactions exposed in air in a controllable manner. In the case of Sn compounds, there is a facile tendency toward oxidation which causes the materials to be doped with Sn⁴⁺ and thus behave as <i>p</i>-type semiconductors displaying metal-like conductivity. The compounds appear to possess very high estimated electron and hole mobilities that exceed 2000 cm²/(V s) and 300 cm²/(V s), respectively, as shown in the case of CH₃NH₃SnI₃ (<b>1</b>). We also compare the properties of the title hybrid materials with those of the “all-inorganic” CsSnI₃ and CsPbI₃ prepared using identical synthetic methods

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties

A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI₃, where A is the methylammonium (CH₃NH₃⁺) or formamidinium (HC­(NH₂)₂⁺) cation and M is Sn (<b>1</b> and <b>2</b>) or Pb (<b>3</b> and <b>4</b>) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of <b>1</b>–<b>4</b> classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that <b>1</b>–<b>4</b> behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25–1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700–1000 nm range (1.1–1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range. The optical properties such as energy band gap, emission intensity, and wavelength can be readily controlled as we show for the isostructural series of solid solutions CH₃NH₃Sn_1–<i>x</i>Pb_<i>x</i>I₃ (<b>5</b>). The charge transport type in these materials was characterized by Seebeck coefficient and Hall-effect measurements. The compounds behave as <i>p</i>- or <i>n</i>-type semiconductors depending on the preparation method. The samples with the lowest carrier concentration are prepared from solution and are <i>n</i>-type; <i>p</i>-type samples can be obtained through solid state reactions exposed in air in a controllable manner. In the case of Sn compounds, there is a facile tendency toward oxidation which causes the materials to be doped with Sn⁴⁺ and thus behave as <i>p</i>-type semiconductors displaying metal-like conductivity. The compounds appear to possess very high estimated electron and hole mobilities that exceed 2000 cm²/(V s) and 300 cm²/(V s), respectively, as shown in the case of CH₃NH₃SnI₃ (<b>1</b>). We also compare the properties of the title hybrid materials with those of the “all-inorganic” CsSnI₃ and CsPbI₃ prepared using identical synthetic methods

Selective Surfaces: Quaternary Co(Ni)MoS-Based Chalcogels with Divalent (Pb²⁺, Cd²⁺, Pd²⁺) and Trivalent (Cr³⁺, Bi³⁺) Metals for Gas Separation

Porous chalcogels with tunable compositions of Co_<i>x</i>M_1<i>–x</i>MoS₄ and Ni_<i>x</i>M_1–<i>x</i>MoS₄, where M = Pd²⁺, Pb²⁺, Cd²⁺, Bi³⁺, or Cr³⁺ and <i>x</i> = 0.3–0.7, were synthesized by metathesis reactions between the metal ions and MoS₄^2–. Solvent exchange, counterion removal and CO₂ supercritical drying led to the formation of aerogels. All chalcogels exhibited high surface areas (170–510 m²/g) and pore volumes in the 0.56–1.50 cm³/g range. Electron microscopy coupled with nitrogen adsorption measurements suggest the presence of both mesoporosity (2 nm < <i>d</i> < 50 nm) and macroporosity (<i>d</i> > 50 nm, where <i>d</i> is the average pore size). Pyridine adsorption corroborated for the acid character of the aerogels. We present X-ray photoelectron spectroscopic and X-ray scattering evidence that the [MoS₄]^2– unit does not stay intact when bound to the metals in the chalcogel structure. The Mo⁶⁺ species undergoes redox reactions during network assembly, giving rise to Mo^4+/5+-containing species where the Mo is bound to sulfide and polysulfide ligands. The chalcogels exhibit high adsorption selectivities for CO₂ and C₂H₆ over H₂, N₂, and CH₄ whereas specific compositions exhibited among the highest CO₂ enthalpy of adsorption reported so far for a porous material (up to 47 kJ/mol). The Co-Pb-MoS₄ and Co-Cr-MoS₄ chalcogels exhibited a 2-fold to 4-fold increase in CO₂/H₂ selectivity compared to ternary CoMoS₄ chalcogels

Structure–Band Gap Relationships in Hexagonal Polytypes and Low-Dimensional Structures of Hybrid Tin Iodide Perovskites

The present study deals with the structural characterization and classification of the novel compounds <b>1</b>–<b>8</b> into perovskite subclasses and proceeds in extracting the structure–band gap relationships between them. The compounds were obtained from the employment of small, 3–5-atom-wide organic ammonium ions seeking to discover new perovskite-like compounds. The compounds reported here adopt unique or rare structure types akin to the prototype structure perovskite. When trimethylammonium (TMA) was employed, we obtained TMASnI₃ (<b>1</b>), which is our reference compound for a “perovskitoid” structure of face-sharing octahedra. The compounds EASnI₃ (<b>2b</b>), GASnI₃ (<b>3a</b>), ACASnI₃ (<b>4</b>), and IMSnI₃ (<b>5</b>) obtained from the use of ethylammonium (EA), guanidinium (GA), acetamidinium (ACA), and imidazolium (IM) cations, respectively, represent the first entries of the so-called “hexagonal perovskite polytypes” in the hybrid halide perovskite library. The hexagonal perovskites define a new family of hybrid halide perovskites with a crystal structure that emerges from a blend of corner- and face-sharing octahedral connections in various proportions. The small organic cations can also stabilize a second structural type characterized by a crystal lattice with reduced dimensionality. These compounds include the two-dimensional (2D) perovskites GA₂SnI₄ (<b>3b</b>) and IPA₃Sn₂I₇ (<b>6b</b>) and the one-dimensional (1D) perovskite IPA₃SnI₅ (<b>6a</b>). The known 2D perovskite BA₂MASn₂I₇ (<b>7</b>) and the related all-inorganic 1D perovskite “RbSnF₂I” (<b>8</b>) have also been synthesized. All compounds have been identified as medium-to-wide-band-gap semiconductors in the range of <i>E</i>_g = 1.90–2.40 eV, with the band gap progressively decreasing with increased corner-sharing functionality and increased torsion angle in the octahedral connectivity