Self-Assembly of Polyhedral Indium–Organic Nanocages

A synthetic strategy to construct discrete indium–organic polyhedra has been illustrated based on small three-membered windows from a 2,5-pyridinedicarboxylate (PDC) ligand with an angle of 120°. [Et₂NH₂]₆[In₆(PDC)₁₂] (<b>InOF-10</b>) is a high-symmetry octahedron with eight three-membered windows, and [Et₂NH₂]₁₈[In₁₈(BPDC)₆(PDC)₃₀] (<b>InOF-11</b>) is a complex polyhedron derived from 3-edge-removed octahedra with an auxiliary biphenyl-3,3′-dicarboxylate (BPDC) ligand. Moreover, the sorption behavior of the latter is also well investigated

An Anionic Uranium-Based Metal–Organic Framework with Ultralarge Nanocages for Selective Dye Adsorption

We herein present a rarely seen (3,4)-connected non-interpenetrated anionic uranium-organic framework with <i>tbo</i> topology (<b>FJI–H-U1</b>), which is constructed from two kinds of ultralarge nanocages. More importantly, <b>FJI–H-U1</b> can selectively adsorb positively charged organic dyes Ethyl Violet, Janus Green B, and Rhodamine B over the anionic organic dye Methyl Orange due to the nature of its anionic framework

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

Constructing Crystalline Heterometallic Indium–Organic Frameworks by the Bifunctional Method

In this work, we systematically report four indium–organic framework (InOF) crystals, which comprise the In­(CO₂)₄ monomer for [InCu­(inc)₄]­(NO₃) (<b>InOF-5</b>) and [Me₂NH₂]₂[In₂(Cu₄I₄)­(pdc)₄] (<b>InOF</b>-<b>6</b>), the In­(OH)­(CO₂)₂ chain for [In₂(Cu₄I₄)­(OH)₂(nia)₄] (<b>InOF-7</b>), and In₃O­(CO₂)₆ clusters for [(In₃O)₂(Cu₄I₄)₃(nia)₁₂(H₂O)₆]­(NO₃)₂ (<b>InOF-8</b>). With the help of the ligand-oriented bifunctional method, a series of novel heterometallic indium–organic frameworks can be easily achieved through the way the pyridyl N-affinitive sites connect to Cu-based units and the COO^–-affinitive sites to In­(III) centers. This new strategy will open the door to the construction of multifunctional and heterometallic InOF materials

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

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

Europium and Terbium Coordination Polymers Assembled from Hexacarboxylate Ligands: Structures and Luminescent Properties

Six lanthanide coordination polymers of the formula [Ln­(L¹)_0.5(H₂O)₂]·2H₂O [where Ln³⁺: Eu³⁺ (<b>1</b>), Tb³⁺ (<b>2</b>), and Gd³⁺(<b>3</b>)] and [Me₂NH₂]­[Ln­(H₂L²)­(H₂O)₄]·0.5DMF·<i>x</i>H₂O [where Ln³⁺: Eu³⁺ (<b>4</b>), Tb³⁺ (<b>5</b>), and Gd³⁺(<b>6</b>)], based on <i>p</i>-terphenyl-2,2″,2‴,5,5″,5‴-hexacarboxylate acid (H₆L¹), and <i>p</i>-terphenyl-3,2″,3″,5,5″,5‴,-hexacarboxylate acid (H₆L²), have been solvothermally synthesized and structurally characterized. Complexes <b>1</b>–<b>3</b> are 3D frameworks exhibiting 6-connected pcu alpha-Po primitive cubic network with topology (4¹².6³), while complexes <b>4</b>–<b>6</b> show two-dimensional (2D) architectures showing simplified 3,4-connected binodal net and (4.6²)­(4².6².8²) topology. Detailed photophysical behaviors have been explored on Eu³⁺, Tb³⁺, and Gd³⁺ complexes. The calculated triplet state energies of H₆L¹ and H₆L² lie above the emissive levels of Eu³⁺ or Tb³⁺ in an ideal range for sensitizing. Furthermore, it is demonstrated that the optimum energy gap between the triplet state of ligand H₆L¹ and the emissive level of Tb³⁺ ion makes the overall quantum yield of Tb³⁺ complex (<b>2</b>) larger than its corresponding Eu³⁺ complex (<b>1</b>). In addition, the coordinated water in the inner sphere has a significant negative influence on the overall quantum yield, especially for the Eu³⁺ complex (<b>4</b>) compared to the Tb³⁺ complex (<b>5</b>), due to the deactivation process caused by vibrational OH oscillators

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