A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

Centimeter-Sized Single Crystal of a One-Dimensional Lead-Free Mixed-Cation Perovskite Ferroelectric for Highly Polarization Sensitive Photodetection

Linear dichroic anisotropic photonic materials are highly attractive due to their great potentials in many applications, which in combination with the ferroelectric properties could broaden their research and applications. However, to date, the linear dichroism conversion phenomenon has not been observed in one-dimensional (1D) large-size single-crystal materials: in particular, lead-free perovskite ferroelectric crystals. Here, we propose a new ferroelectric design strategy: namely, partial organic cation substitution for precisely designing 1D polarization-sensitive perovskite ferroelectrics. As an example, the 1D mixed-cation perovskite ferroelectric (n-propylammonium)­(methylammonium)­SbBr5 was synthesized, which exhibits a fascinating ferroelectricity with a notable reversible polarization of 2.9 μC/cm2 and a large ferroelectricity-driven polarization ratio of 6.9. Importantly, the single-crystalline photodetectors also exhibit superior optoelectronic anisotropic performances at the paraelectric phase, having a large photoelectric anisotropy ratio (∼35), an excellent polarization-sensitive dichroism ratio (∼1.31), highly sensitive detectivity up to ∼109 Jones, and a fast response rate (∼45/68 μs). This finding provides a significant and effective pathway for the targeted design of new functional lead-free linear dichroic anisotropic photonic ferroelectrics

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

A Series of Lanthanide Secondary Building Units Based Metal−Organic Frameworks Constructed by Organic Pyridine-2,6-Dicarboxylate and Inorganic Sulfate

A series of novel lanthanide coordination polymers constructed from organic pyridine-2,6-dicarboxylate (2,6-pydc) and inorganic sulfate, namely, [Eu3(2,6-pydc)3(2,6-Hpydc)(SO4)(H2O)3·(H2O)3] (1), [Ln2(2,6-pydc)2(SO4)(H2O)2·(H2O)2] (Ln = Ce (2); Ln = Pr (3); Ln = Nd (4); Ln = Sm (5)), and [Ce5(2,6-pydc)6(SO4)2(H2O)3·(Me2NH2)] (6), have been synthesized under hydrothermal conditions. X-ray crystal structure analyses reveal that these compounds have a rich structural chemistry. Compound 1 presents a four-connected two-dimensional (2D) network based on hexanuclear {Eu6} secondary building units (SBUs). The 2D layers are further linked into a three-dimensional (3D) supramolecular framework via strong π−π stacking interactions of the pyridyl rings. Compounds 2−5 are isostructural and adopt uninodal six-connected 3D framework of pcu topology constructed from square-planar tetranuclear {Ln4} SBUs. Of particular interest is that compound 6 exhibits a protonated (Me2NH2)+ templated binodal (4,6)-connected 3D anionic framework with (42510728)(4254) topology, when the Ce(3) monomer and the planar tetranuclear {Ce4} SBUs are regarded as four-connected and six-connected nodes, respectively. Notably, sulfate serves as an auxiliary supporting bridge to strengthen the {Ln4} or {Ln6} SBUs in these compounds. Compound 1 displays intense red luminescence and exhibits the characteristic transition of the Eu3+ ion. The magnetic properties of 1, 4, and 5 reveal the weak antiferromagnetic characters. Furthermore, infrared (IR), thermogravimetric analysis (TGA), elemental analyses (EA), and powder X-ray diffraction (PXRD) properties of these compounds are also studied

Effect of Lanthanide Contraction on Crystal Structures of Three-Dimensional Lanthanide Based Metal–Organic Frameworks with Thiophene-2,5-Dicarboxylate and Oxalate

Six three-dimensional (3D) lanthanide coordination polymers with formula [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1, Nd 2, Sm 3, Gd 4) and [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (2Ln) (Ln = Dy 5, Er 6) have been synthesized by hydrothermal reactions of thiophene-2,5-dicarboxylate (TDC) and oxalate (ox) with corresponding lanthanide nitrate. X-ray crystal structure analyses reveal that 1Ln and 2Ln are isomers that may be produced by lanthanide contraction. Compounds 1–4 are isostructural and possess binodal (4,5)-connected 3D framework of tcj/hc topology with triangular channels along the [101] direction. Isostructural compounds 5 and 6 present trinodal (4,4,6)-connected 3D framework of sqc254 topology with rectangular channels along the b axis. The magnetic properties reveal that compound 2 has antiferromagnetic behavior, while compound 4 has ferromagnetic behavior. The luminescent property shows that compound 5 displays intense yellow luminescence and exhibits the typical Dy3+ ion emission. Furthermore, infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA), powder X-ray diffraction (PXRD), magnetic and luminescent properties of these compounds are also investigated

Effect of Lanthanide Contraction on Crystal Structures of Three-Dimensional Lanthanide Based Metal–Organic Frameworks with Thiophene-2,5-Dicarboxylate and Oxalate

Six three-dimensional (3D) lanthanide coordination polymers with formula [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1, Nd 2, Sm 3, Gd 4) and [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (2Ln) (Ln = Dy 5, Er 6) have been synthesized by hydrothermal reactions of thiophene-2,5-dicarboxylate (TDC) and oxalate (ox) with corresponding lanthanide nitrate. X-ray crystal structure analyses reveal that 1Ln and 2Ln are isomers that may be produced by lanthanide contraction. Compounds 1–4 are isostructural and possess binodal (4,5)-connected 3D framework of tcj/hc topology with triangular channels along the [101] direction. Isostructural compounds 5 and 6 present trinodal (4,4,6)-connected 3D framework of sqc254 topology with rectangular channels along the b axis. The magnetic properties reveal that compound 2 has antiferromagnetic behavior, while compound 4 has ferromagnetic behavior. The luminescent property shows that compound 5 displays intense yellow luminescence and exhibits the typical Dy3+ ion emission. Furthermore, infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA), powder X-ray diffraction (PXRD), magnetic and luminescent properties of these compounds are also investigated