Thiacalix[4]arene-Supported Kite-Like Heterometallic Tetranuclear Zn^IILn^III₃ (Ln = Gd, Tb, Dy, Ho) Complexes

Four kite-like tetranuclear Zn^IILn^III₃ (Ln= Gd <b>1</b>, Tb <b>2</b>, Dy <b>3</b>, Ho <b>4</b>) clusters supported by <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene (H₄BTC4A) have been prepared under solvothermal conditions and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction (PXRD). In the structures of these four complexes, each of them is capped by two tail-to-tail <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene molecules to form a bent sandwich-like unit. The photoluminescent analyses reveal that the H₄BTC4A is an efficient sensitizer for Tb³⁺ ions in <b>2</b>. The magnetic properties of complexes <b>1</b>–<b>4</b> are also investigated, in which complex <b>3</b> exhibits slow magnetization relaxation typical for single molecule magnets

Thiacalix[4]arene-Supported Kite-Like Heterometallic Tetranuclear Zn^IILn^III₃ (Ln = Gd, Tb, Dy, Ho) Complexes

Four kite-like tetranuclear Zn^IILn^III₃ (Ln= Gd <b>1</b>, Tb <b>2</b>, Dy <b>3</b>, Ho <b>4</b>) clusters supported by <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene (H₄BTC4A) have been prepared under solvothermal conditions and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction (PXRD). In the structures of these four complexes, each of them is capped by two tail-to-tail <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene molecules to form a bent sandwich-like unit. The photoluminescent analyses reveal that the H₄BTC4A is an efficient sensitizer for Tb³⁺ ions in <b>2</b>. The magnetic properties of complexes <b>1</b>–<b>4</b> are also investigated, in which complex <b>3</b> exhibits slow magnetization relaxation typical for single molecule magnets

Thiacalix[4]arene-Supported Kite-Like Heterometallic Tetranuclear Zn^IILn^III₃ (Ln = Gd, Tb, Dy, Ho) Complexes

Four kite-like tetranuclear Zn^IILn^III₃ (Ln= Gd <b>1</b>, Tb <b>2</b>, Dy <b>3</b>, Ho <b>4</b>) clusters supported by <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene (H₄BTC4A) have been prepared under solvothermal conditions and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction (PXRD). In the structures of these four complexes, each of them is capped by two tail-to-tail <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene molecules to form a bent sandwich-like unit. The photoluminescent analyses reveal that the H₄BTC4A is an efficient sensitizer for Tb³⁺ ions in <b>2</b>. The magnetic properties of complexes <b>1</b>–<b>4</b> are also investigated, in which complex <b>3</b> exhibits slow magnetization relaxation typical for single molecule magnets

Self-Assembly of Thiacalix[4]arene-Supported Nickel(II)/Cobalt(II) Complexes Sustained by in Situ Generated 5-Methyltetrazolate Ligand

Solvothermal reactions of thiacalix[4]­arene, NaN₃, and acetonitrile in the presence of nickel­(II)/cobalt­(II) salts yielded four discrete complexes sustained by the in situ generated 5-methyltetrazolate ligand, [Ni^II₁₂(PTC4A)₃(μ₆-CO₃)₂(μ-Mtta)₂(μ-Mtta)₄ (μ₄-Mtta)₂(Py)₄]·7DMF·2Py·dma (<b>1</b>), [Co^II₁₂(PTC4A)₃(HCOO)₃(μ₆-CO₃)₂ (μ-Mtta)­(μ-Mtta)₂(μ₄-Mtta)₂(Py)₄]·5DMF·dma (<b>2</b>), [Co^II₁₂(BTC4A)₃(HCOO)₂ (μ₆-CO₃)₂(μ-Mtta)₄(μ₄-Mtta)₂(dma)₂(Pz)₂]·2DMF·3dma (<b>3</b>), and [Co^II₁₆(BTC4A)₄(μ₄-Cl)₄ (HCOO)₂(μ-Mtta)₆(μ-Mtta)₈]·10DMF·6CH₃CN·4Hdma (<b>4</b>) (H₄PTC4A = <i>p</i>-phenylthiacalix­[4]­arene; H₄BTC4A = <i>p</i>-tert-butylthiacalix­[4]­arene; HMtta = 5-methyl tetrazolate). Crystal structural analyses revealed that complexes <b>1</b>–<b>3</b> are stacked by pseudotrigonal planar entities, which consist of three metal^II₄-thiacalix­[4]­arene subunits including two shuttlecock-like and one cylinder-like ones. These subunits are connected in an up-to-down-to-up fashion through six different 5-methyl tetrazolate anions. Both the in situ generated 5-methyl tetrazolate anion and carbonato anion play an important role in constructing these high-nuclearity clusters. When the corresponding chloride salt was used as precursors in the synthesis, complex <b>4</b> was obtained, which is stacked by wheel-like entities possessing four shuttlecock-like building blocks linked by eight in situ generated 5-methyl tetrazolate ligands in an up-to-up fashion. The differences in the structures of complexes <b>3</b> and <b>4</b> indicate that the geometry and size of the corresponding anions together with their coordinating properties are essential in determining the final structures. The magnetic properties of complexes <b>1</b>–<b>4</b> were examined, indicating strong antiferromagnetic interactions between the nickel­(II)/cobalt­(II) ions in the temperature range of 50–300 K

Self-Assembly of Thiacalix[4]arene-Supported Nickel(II)/Cobalt(II) Complexes Sustained by in Situ Generated 5-Methyltetrazolate Ligand

Solvothermal reactions of thiacalix[4]­arene, NaN₃, and acetonitrile in the presence of nickel­(II)/cobalt­(II) salts yielded four discrete complexes sustained by the in situ generated 5-methyltetrazolate ligand, [Ni^II₁₂(PTC4A)₃(μ₆-CO₃)₂(μ-Mtta)₂(μ-Mtta)₄ (μ₄-Mtta)₂(Py)₄]·7DMF·2Py·dma (<b>1</b>), [Co^II₁₂(PTC4A)₃(HCOO)₃(μ₆-CO₃)₂ (μ-Mtta)­(μ-Mtta)₂(μ₄-Mtta)₂(Py)₄]·5DMF·dma (<b>2</b>), [Co^II₁₂(BTC4A)₃(HCOO)₂ (μ₆-CO₃)₂(μ-Mtta)₄(μ₄-Mtta)₂(dma)₂(Pz)₂]·2DMF·3dma (<b>3</b>), and [Co^II₁₆(BTC4A)₄(μ₄-Cl)₄ (HCOO)₂(μ-Mtta)₆(μ-Mtta)₈]·10DMF·6CH₃CN·4Hdma (<b>4</b>) (H₄PTC4A = <i>p</i>-phenylthiacalix­[4]­arene; H₄BTC4A = <i>p</i>-tert-butylthiacalix­[4]­arene; HMtta = 5-methyl tetrazolate). Crystal structural analyses revealed that complexes <b>1</b>–<b>3</b> are stacked by pseudotrigonal planar entities, which consist of three metal^II₄-thiacalix­[4]­arene subunits including two shuttlecock-like and one cylinder-like ones. These subunits are connected in an up-to-down-to-up fashion through six different 5-methyl tetrazolate anions. Both the in situ generated 5-methyl tetrazolate anion and carbonato anion play an important role in constructing these high-nuclearity clusters. When the corresponding chloride salt was used as precursors in the synthesis, complex <b>4</b> was obtained, which is stacked by wheel-like entities possessing four shuttlecock-like building blocks linked by eight in situ generated 5-methyl tetrazolate ligands in an up-to-up fashion. The differences in the structures of complexes <b>3</b> and <b>4</b> indicate that the geometry and size of the corresponding anions together with their coordinating properties are essential in determining the final structures. The magnetic properties of complexes <b>1</b>–<b>4</b> were examined, indicating strong antiferromagnetic interactions between the nickel­(II)/cobalt­(II) ions in the temperature range of 50–300 K

A Series of Octanuclear-Nickel(II) Complexes Supported by Thiacalix[4]arenes

A series of discrete complexes, [Ni₈(BTC4A)₂(μ₆-CO₃)₂(μ-CH₃COO)₄(dma)₄]·H₂O (<b>1</b>), [Ni₈(BTC4A)₂(μ₆-CO₃)₂(μ-Cl)₂(μ-HCOO)₂(dma)₄]·2DMF·2CH₃CN (<b>2</b>), [Ni₈(PTC4A)₂ (μ₆-CO₃)₂(μ-CH₃COO)₄(dma)₄]·DMF (<b>3</b>), and [Ni₈(PTC4A)₂(μ₆-CO₃)₂(μ-OH)­(μ-HCOO)₃ (dma)₄] (<b>4</b>) (<i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene = H₄BTC4A, <i>p</i>-phenylthiacalix­[4]­arene = H₄PTC4A, dma = dimethylamine, and DMF = <i>N</i>,<i>N</i>′-dimethylformamide), have been prepared under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses, powder XRD, and IR spectroscopy. These four complexes are stacked by dumbbell-like building blocks with one chairlike octanuclear-nickel­(II) core, which is capped by two thiacalix[4]­arene molecules and connected by two in situ generated carbonato anions and different auxiliary anions. This work implied that not only the solvent molecules but also the upper-rim groups of thiacalix[4]­arenes have significant effects on the self-assembly of the dumbbell-like building blocks. The magnetic properties of complexes <b>1</b>–<b>4</b> were examined, indicating strong antiferromagnetic interactions between the nickel­(II) ions in the temperature range of 50–300 K

A Family of Highly Efficient CuI-Based Lighting Phosphors Prepared by a Systematic, Bottom-up Synthetic Approach

Copper­(I) iodide (CuI)-based inorganic–organic hybrid materials in the general chemical formula of CuI­(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI­(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials’ crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic–organic hybrid materials

A Family of Highly Efficient CuI-Based Lighting Phosphors Prepared by a Systematic, Bottom-up Synthetic Approach

Copper­(I) iodide (CuI)-based inorganic–organic hybrid materials in the general chemical formula of CuI­(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI­(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials’ crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic–organic hybrid materials

A Family of Highly Efficient CuI-Based Lighting Phosphors Prepared by a Systematic, Bottom-up Synthetic Approach

Copper­(I) iodide (CuI)-based inorganic–organic hybrid materials in the general chemical formula of CuI­(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI­(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials’ crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic–organic hybrid materials

A Family of Highly Efficient CuI-Based Lighting Phosphors Prepared by a Systematic, Bottom-up Synthetic Approach

Copper­(I) iodide (CuI)-based inorganic–organic hybrid materials in the general chemical formula of CuI­(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI­(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials’ crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic–organic hybrid materials