Structure and photoluminescent property of a three-dimensional pillared-layer La(III)-Cu(I) heterometallic coordination polymer

A three-dimensional (3D) pillared-layer La(III)-Cu(I) heterometallic coordination polymer (HCP) formulated as [La₂Cu₄I₃(Hina)₇(H₂O)] _n (1) (Hina = isonicotinic acid), is synthesized by a hydrothermal reaction of La₂O₃, CuI, and ina. The crystal structure is determined by single crystal X-ray diffraction. HCP 1 crystallizes in the monoclinic space group P2₁/c with unit cell parameters: a = 17.0147(3) Å, b = 18.4431(3) Å, c = 16.7487(3) Å, β = 102.469(2)°, V = 5131.84(15) ų, Z = 4. It features a 3D pillared-layer heterometallic organic framework, where Ln-ina layers are pillared by discrete [Cu₈I₆(ina)₁₂] units along the direction of the a axis. In addition, the solid-state photoluminescent property is investigated.     

Sonochemical synthesis and characterization of a nanostructured 3-D lead(II) coordination polymer with 4-methoxybenzoyltrifluoroacetone

Nanoparticles of a 3-D coordination polymer, [Pb₂(mbtfa)₄] _n (1) (Hmbtfa?=?4-methoxybenzoyltrifluoroacetone), have been synthesized by a sonochemical method. The nanomaterial was characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy, and elemental analyses. Compound 1 was structurally characterized by single-crystal X-ray diffraction. The structure of 1 shows the compound is triclinic and consists of 3-D polymeric units.     

An unusual mixed-valence Cu(I)-Cu(II) 3-D framework

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.     

Assembly of a two-dimensional oxalate-bridged heterometallic Co(II)(3)Cr(III)(2) coordination polymer

Reaction of CoCl(2).4H(2)O with Ag(3)[Cr(ox)(3)] (3 : 2 mol/mol) in methanol gives rise to an oxalate-bridged complex [Co(MeOH)(2)](3)[Cr(ox)(3)](2).6MeOH that consists of a rare cloverleaf-like layered structure (12,3-net). Ferromagnetic coupling is operative between the adjacent metal ions through the oxalate bridges.     

New porphyrin-based metal-organic framework with high porosity: 2-D infinite 22.2-A square-grid coordination network

A new 2-D coordination network with 22.2-A square-grid coordination networks was prepared from a dicopper(II) tetraacetate [Cu2(AcO)4] as a linear linker motif and 5,10,15,20-tetra-4-pyridyl-21H,23H-porphine (H2TPyP) as a four-connected vertex, forming a regular high-porous structure. The characterization by N2 adsorption indicated that this coordination network has uniform micropores and gas adsorption cavities.     

Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(I)-Cu(II) coordination polymer including pyrrolidine dithiocarbamate ligand

A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σμ～ 0.4 cm(2) V(-1) s(-1).     

New oxamato-bridged trinuclear Cu(II)-Cu(II)-Cu(II) complexes with hydrogen-bond supramolecular structures: synthesis and magneto-structural studies

Three oxamato-bridged copper(II) complexes of formula [(Cu(H(2)O)(tmen)Cu(tmen))(mu-Cu(H(2)O)(Me(2)pba))](n)((PF(6))(2))(n).2nH(2)O (1), [(Cu(H(2)O)(tmen)Cu(NCS)(tmen))(mu-Cu(H(2)O)(Me(2)pba))](2)(ClO(4))(2).4H(2)O (2), and [(Cu(H(2)O)(tmen)Cu(NCS)(tmen))(mu-Cu(H(2)O)(Me(2)pba))](2)(PF(6))(2).4H(2)O (3), where Me(2)pba = 2,2-dimethyl-1,3-propylenebis(oxamato) and tmen = N,N,N',N'-tetramethylethylenediamine, have been synthesized and characterized. Their crystal structures were solved. Complex 1 crystallizes in the monoclinic system, space group P2(1), with a = 15.8364(3) A, b =8.4592(2) A, c = 15.952 A, beta = 101.9070(10) degrees, and Z = 2. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 6.69530(10) A, b = 18.2441(3) A, c = 31.6127(5) A, beta = 90.1230(10) degrees, and Z = 4. Complex 3 crystallizes in the monoclinic system, space group P2(1)/c, with a = 6.68970(10) A, b = 18.150 A, c = 32.1949(4) A, beta = 90.0820(10) degrees, and Z = 4. The three complexes have a central core in common: a trinuclear Cu(II) complex with the two terminal Cu(II) ions blocked by N,N,N',N'-tetramethylethylenediamine. The structure of complex 1 consists of trinuclear cationic entities connected by hydrogen bonds to produce a supramolecular one-dimensional array. The structure of complexes 2 and 3 consist of trinuclear cationic entities linked by pairs by hydrogen bonds between the water molecule of the central Cu(II) and one oxygen atom of the oxamato ligand of the neighboring entity, forming a hexanuclear complex. The magnetic properties of the three complexes were studied by susceptibility vs temperature measurement. For complexes 1-3 the fit was made by the irreducible tensor operator (ITO). The values obtained were J(1) = -386.48 cm(-1) and J(2) = 1.94 cm(-1) for 1, J(1) = -125.77 cm(-1) and J(2) = 0.85 cm(-1) for 2, and J(1) = -135.50 cm(-1) and J(2) = 0.94 cm(-1) for 3. In complex 1, the coordination polyhedron of the terminal Cu(II) atoms can be considered as square pyramidal; the apical positions are filled by the oxygen atom from a water molecule in the former and a F atom of the hexafluorophosphate anion in the latter showing a quasi-planar [Cu(CuMe(2)pba)Cu] network. For complexes 2 and 3, the square pyramidal environment of the terminal Cu(II) ions was strongly modified. To our knowledge, this is the first time that the longest distance (apical) in complexes with oxamato derivatives and bidentate amines as blocking ligands has been reported in one of the oxamato arms. The great difference in J(1) values between 1 and the other two complexes is interpreted as an orbital reversal of the magnetic orbitals of the terminal Cu(II) ions in 2 and 3.     

Functional ruthenium(II)- and iridium(III)-containing polymers for potential electro-optical applications

The need for novel materials with luminescent properties and advanced processing features requires reliable and reproducible synthetic routes for the design of suitable materials, such as e.g. polypyridyl ruthenium(II) and iridium(III)-containing polymers. The most popular ligand for those purposes is the 4,4'-functionalized bipyridine unit. Therefore, several synthetic strategies for the derivatization of the 4,4'-dimethyl-2,2'-bipyridine are highlighted, and in particular functionalities, which enable further covalent linkage to polymeric structures, are discussed in this critical review. Subsequently, the different synthetic strategies for the preparation of polymeric metal-complexes are described, either starting from small functionalized complexes (later covalently attached to the polymer), or from macroligands (subsequently coordinated to the metal ions). The designed materials reveal good processing properties using spin coating and inkjet printing, as well as beneficial electro-optical properties for potential thin functional film applications, such as light-emitting electrochemical cells.     

A 3D chiral porous In(III) coordination polymer with PtS topological net

The solvothermal reaction of In(III) and 1,2,4,5-benzeneteracarboxylic acid with the presence of piperazine leads to the generation of a novel 3D chiral porous coordination polymer with PtS topological net. Interestingly, the resulting crystals were not a racemic mixture but enantiomeric excess, which was confirmed by the measurement of optical rotation of bulk samples using solid vibrational circular dichroism (VCD) spectra and the solid circular dichroism (CD) spectra based on large crystals from one crystallization. High-pressure CO(2) and CH(4) adsorption measurement at 298 K reveals that activated 1 can absorb 45.8 cm(3) (STP)/g CO(2) at 22 atm and 22.5 cm(3) (STP)/g CH(4) at 25 atm.     

Synthesis,crystal structure,and spectral analysis of a 1-D Mn(II) coordination polymer

A manganese(II) coordination polymer [Mn(TMB)₂?·?H₂O] _n (1) (HTMB?=?3,4,5-trimethoxybenzoic acid) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, powder X-ray diffraction analysis, spectroscopic (IR, solid state UV-Vis), and thermal methods. The crystal belongs to orthorhombic system, space group P2₁2₁2₁, with cell parameters a?=?7.3001(8), b?=?11.4146(13), c?=?27.053(3)?Å, α?=?β?=?γ?=?90°, V?=?2254.3(4)?ų, Z?=?4. In 1, TMB in two different coordination modes bridges six-coordinate manganese(II) centers forming a 1-D infinite chain coordination framework. The spectral and thermal properties of the complexes have also been studied.     

Cu(II)-脱乙酰壳聚糖配位聚合物的配位数

IR,ESR和XPS的测试结果表明,脱乙酰壳聚糖(简记CS)膜在铜氨水溶液浸渍过程中Cu(II)既与CS发生配位反应形成Cu(II)-CS配位聚合物,也产生吸附作用。ESR谱示出CuCl~2.2H~2O与Cu(II)-CS膜中的Cu(II)均含有一个单电子,可以利用XPS的Shake-up效应研究Cu(II)-CS配位聚合物的配位数,所得结果为4。又以同样的方法研究Cu(II)-聚乙烯醇(简记PVA)配位聚合物的配位数,发现Cu(II)是以低自旋状态的dsp^2杂化空轨道与PVA的羟基氧配位,其配位数也是4,这与资料所报道的一致,从而间接地验证了此方法研究Cu(II)-CS配位聚合物配位数的可靠性。     

Sequestering aromatic molecules with a spin-crossover Fe(II) microporous coordination polymer

All in a spin: A series of three-dimensional porous coordination polymer {Fe(dpe)[Pt(CN)(4)]}?G (dpe = 1,2-di(4-pyridyl)ethylene; G = phenazine, anthracene, or naphthalene) exhibiting spin crossover and host-guest functions is reported. The magnetic properties of the framework are very sensitive to the chemical nature (aromatic or hydroxilic solvents) and the size of the included guest molecules.     

A lead(II) coordination polymer containing 2-carboxycinnamic acid and 1,10-phenanthroline and its 3-D supramolecular network

The coordination polymer {[Pb(cca)(phen)]H₂O} _n (H₂cca?=?2-carboxycinnamic?acid and phen?=?1,10-phenanthroline) was synthesized by hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. The complex possesses a 1-D chain structure composed of infinite Pb-cca-Pb linkages, in which the [PbO₄N₂] subunits are linked by bridging cca in bis(chelating-bridging) coordination mode. The coordination around the lead(II) is hemi-directed and weak Pb···O interactions are observed that result in a double-chain structure. The chains are combined to generate a 3-D supramolecular structure through interchain C–H···π, C–H···O, and π···π stacking interactions. Fluorescence of the complex originates from π*–π transitions of the ligand.     

Unprecedented ferromagnetic interaction in an erbium(III)–copper(II) coordination polymer

Two 3D Ln(III)–Cu(II) coordination polymers [Er₂Cu₃(pydc)₆(H₂O)₆]_n (1) and [Tb₂Cu₃(pydc)₆(H₂O)₆]_n (2) were hydrothermally prepared from pyridine-2,4-dicarboxylic acid (H₂pydc) and characterized by single-crystal X-ray diffraction analysis. The magnetic studies show that an unexpected ferromagnetic interaction between metal centers exists in 1 while 2 behaves as an antiferromagnet.     

A porous supramolecular architecture from a copper(II) coordination polymer with a 3D four-connected 8(6) net

A novel coordination polymer [[Cu(L(1))(L(2))(H(2)O)].5H(2)O](n) (1), where L(1) =1,1'-(1,4-butanediyl)bis(imidazole) and L(2) = m-phthalate anion, has been obtained by using an unusual crystallization process. It crystallizes in the orthorhombic space group Pna2(1), which belongs to the crystal class mm2, with a = 9.0521(18), b = 15.401(3), and c = 17.141(3) A, alpha = beta = gamma = 90 degrees, V = 2389.7(8) A(3), and Z = 4. The complex 1 composing a porous supramolecular architecture displays unprecedented four-connected topology of an 8(6) net in coordination polymer chemistry. Thermal gravimetric analysis (TGA) and X-ray powder diffraction (XRPD) patterns for 1 are discussed in detail.     

Uranyl sensitization of samarium(III) luminescence in a two-dimensional coordination polymer

Heterometallic carboxyphosphonates UO(2)(2+)/Ln(3+) have been prepared from the hydrothermal reaction of uranyl nitrate, lanthanide nitrate (Ln = Sm, Tb, Er, Yb), and phosphonoacetic acid (H(3)PPA). Compound 1, (UO(2))(2)(PPA)(HPPA)(2)Sm(H(2)O)·2H(2)O (1) adopts a two-dimensional structure in which the UO(2)(2+) metal ions bind exclusively to the phosphonate moiety, whereas the Ln(3+) ions are coordinated by both phosphonate and carboxylate functionalities. Luminescence studies of 1 show very bright visible and near-IR samarium(III)-centered emission upon direct excitation of the uranyl moiety. The Sm(3+) emissive state exhibits a double-exponential decay with lifetimes of 67.2 ± 6.5 and 9.0 ± 1.3 μs as measured at 594 nm, after excitation at both 365 and 420 nm. No emission is observed in the region typical of the uranyl cation, indicating that all energy is either transferred to the Sm(3+) center or lost to nonradiative processes. Herein we report the synthesis, crystal structure, and luminescent behavior of 1, as well as those of the isostructural terbium, erbium, and ytterbium analogues.     

Guest-induced crystal-to-crystal expansion and contraction of a 3-D porous coordination polymer

A silver(I) 3-D porous coordination polymer (PCP, 1) with a sodalite topology undergoes a remarkable reversible crystal-to-crystal expansion and contraction upon exposure to different solvents. Notably, complete desolvation of 1 also facilitates a transformation to a non-porous 2-D coordination polymer (2).