4f Heterometallic Coordination Polymers Research Articles

A 3-D pillar-layered coordination polymer {[EuCu(C2O4)(na)2] · 2H2O} n : synthesis, structure and photoluminescent properties

A 3d–4f heterometallic coordination polymer, {[EuCu(C2O4)(na)2] · 2H2O} n (1) [Hna=nicotinic acid], has been synthesized by hydrothermal reaction of lanthanide oxides, Cu(I), and pyridine-2,3-dicarboxylic acid. 1 features a 3-D pillar-layered coordination framework constructed from two-dimensional lanthanide-carboxylate layers and Cu(na) pillars. Interestingly, the na ligand was obtained by the in situ decarboxylation of pyridine-2,3-dicarboxylic acid.

Construction of three-dimensional Ln–Ag (Ln = Eu; Tm) coordination polymers based on isonicotinate and oxalate ligands

Hexanuclear 4d–4f heterometallic coordination polymers, [Ln 2Ag 4(IN) 5(ox) 2(NO 3)(H 2O) 2 · 3H 2O] [Ln = Eu ( 1), Tm ( 2); IN = isonicotinate and ox = oxalate], have been synthesized by hydrothermal reaction of mixed organic ligands and metal salts. Both structures display the same unusual 3D heterometallic coordination frameworks based on rare zigzag lanthanide–oxalate–silver chains, Ag 2(IN) 3 units and IN linkers. The photoluminescent properties of complex 2 were studied.

A novel 3D 4d–4f heterometallic coordination polymer: Synthesis, crystal structure and luminescence

A novel 4d–4f heterometallic coordination polymer [EuAg(imdc) 2] n ( 1) (imdc = imidazoledicarboxylate) has been hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. X-ray single-crystal structural analysis reveals that 1 is a three-dimensional framework. Furthermore, 1 also displayed photoluminescent properties in the red range at room temperature.

A novel three-dimensional 3d–4f heterometallic coordination polymer: Crystal structure and photoluminescence

A novel 3d–4f heterometallic coordination polymer {[ZnEu(PDA) 2(BDC) 1/2(H 2O)] · 2H 2O} n (PDA = pyridine-2,5-dicarboxylate, BDC = 1,4-benzenedicarboxylate) ( 1) has been synthesized by hydrothermal method. PDA ligands adopt two kinds of coordination modes to bridge Eu(III) and Zn(II) ions into two types of 2D layers, respectively, which further intersect at Eu(III) ions and form a 3D network. BDC ligands act as a linear linker to bridge the Eu(III) ions from adjacent layers, resulting in the final 3D network. The photoluminescent behavior indicates that the introduction of Zn ions in the 3-D polymeric fragment slightly enhances the luminescent lifetime and quantum efficiency.

Construction of an unusual three-dimensional transition metal lanthanide Ln/Cu(Br/Cl) coordination polymer with isonicotinate as the single ligand

A 3d–4f heterometallic coordination polymer, {[Cu 10Er 4(IN) 14ClBr 7(H 2O) 10] · 2H 2O} n ( 1) [IN = isonicotinate], has been synthesized by hydrothermal reaction of the ligand with CuBr 2, NaCl and Er 2O 3. Complex 1 represents a rare 3D heterometallic coordination framework constructed from Er-carboxylate subunits and unique Cu-halide (Br/Cl) chains that are bridged by a single type of linear ligand. Furthermore, the luminescent properties of complex 1 have also been investigated.

Twofold interpenetration corrugated brick wall frameworks of 3d−4f heterometallic coordination polymers

Two 3d−4f heterometallic coordination polymers [EuCo(pydc) 3(H 2O) 3] n · 2 nH 2O ( 1) [YbCo(pydc) 3(H 2O) 3] n · nH 2O ( 2) have been hydrothermally synthesized from pyridine-2,4-dicarboxylic acid (H 2pydc). Compounds 1 and 2 possess isostructural twofold interpenetration corrugated brick wall layer structures with (6,3) topology.

Synthesis and Characterization of Three-Dimensional 3d−3d and 3d−4f Heterometallic Coordination Polymers with High Thermal Stability

Using 1,2-bis(4-pyridyl)ethane (bpe) and benzene-1,3-biscarboxylic acid (H2bba) as ligands, two novel heterometallic three-dimensional coordination polymers {[Zn3Mn1.5(bpe)(bba)4(Hbba)]·bpe}n (Mn−Zn) and {[Zn2Pr(bpe)(bba)3(Hbba)]·H2O}n (Pr−Zn) were isolated under hydrothermal conditions. Both complexes are constructed via 3d−3d and 3d−4f clusters as secondary building units, respectively, which represent the first template synthesis for 3D heterometallic MOFs.

A unique 3-D 3d–4f heterometallic coordination polymer with double betaine ligand: Crystal structure and magnetic properties

A unique 3d–4f heterometallic coordination polymer with double betaine ligand, [GdCu 2(L 1) 4(H 2O) 2](ClO 4) 7 · 6H 2O 1 (L 1 = 1,3-bis(pyridinio-4-carboxylato)-propane), has been synthesized by the self-assembly of Cu(ClO 4) 2 and Gd(ClO 4) 3 with flexible double betaine ligand L 1, and structurally characterized by single-crystal X-ray diffraction. The structure of 1 can be regarded as being constructed by the cross-linkage of the vertex-sharing double-paddle-wheel-like trinuclear [Cu(COO) 4Gd(COO) 4Cu] units and L 1 ligands to produce an interesting cationic NaCl-like framework with a 4 126 3 topology, which is counter-balanced by the perchlorate ions located in the interspaces of the framework. Variable-temperature magnetic susceptibilities of 1 show there is no magnetic interaction between the Cu(II) and Gd(III) ions.

3D Heterometallic (3d–4f) coordination polymers: A ferromagnetic interaction in a Gd(III)–Cu(II) couple

Four 3d–4f heterometallic coordination polymers, [Cu3(IDA)6Ln2]·n(H2O) [IDA= iminodiacetate dianion; Ln=Gd, n=3 (1); Ln=Nd, n=6 (2); Ln=Sm, n=6 (3)] and [Cu(Cl)(NTA)Sm(H2O)6]·(ClO4)·(H2O) (4) [NTA=nitrilotriacetate trianion], have heen synthesized and characterized by single crystal X-ray diffraction analysis. Complexes 1–3 are isomorphous, showing a 3D coordination framework having tubular channels filled by lattice water molecules running parallel to the c axis. Whereas complex 4 is a 1D polymer of alternating copper and samarium ions connected by NTA, and the chains get involved in H-bonding interactions resulting in a 3D network. A low temperature magnetic study reveals ferromagnetic interactions for complex 1. Thermogravimetric and X-ray powder diffraction analyses of 1, 2 and 3 show that the covalently bonded 3D network remains almost unaffected after deaquation.

Self-assembly of 3-D 4d–4f coordination frameworks based on 1-D inorganic heterometallic chains and linear organic linkers

Four novel 4d–4f heterometallic coordination polymers, namely, LnAg(pydc)2(Hnic)0.5 [Ln = Nd (1), Eu (2); H2pydc = pyridine-3,4-dicarboxylic acid, Hnic = nicotinic acid], and LnAg(inic)2(nicO)·0.5H2O [Ln = Nd (3), Eu (4); Hinic = isonicotinic acid, H2nicO = 2-hydroxynicotinic acid], have been synthesized and characterized. Compounds 1 and 2 exhibit three-dimensional (3-D) coordination frameworks constructed by one-dimensional (1-D) inorganic heterometallic chains and linear pydc linkers. The 1-D channels occupied by disordered Hnic molecules emerge. To our knowledge, both compounds represent the first examples of 3-D open-framework 4d–4f heterometallic coordination frameworks. Compounds 3 and 4 display 3-D covalent frameworks composed of 1-D inorganic heterometallic chains joined by inic ligands, representing the first examples of 3-D 4d–4f coordination frameworks constructed by inorganic heterometallic chain and mixed linear and nonlinear ligands with same donors. Furthermore, the luminescent properties of 2 and 4 were studied.

Selected Controlled Synthesis of Three-Dimensional 4d−4f Heterometallic Coordination Frameworks by Lanthanide Carboxylate Subunits and Silver Centers

By control of mixed ligands with particular coordination sites, three novel three-dimensional (3D) 4d−4f heterometallic coordination polymers, [Ln4(H2O)2Ag(1,3-bdc)4(inic)5]·nH2O (Ln = Nd (1), n = 0.25; Eu (2), n = 0; 1,3-H2bdc = 1,3-benzenedicarboxylic acid and Hinic = isonicotinic acid) and [Nd(H2O)Ag(1,2-bdc)(inic)2] (3) (1,2-H2bdc = 1,2-benzenedicarboxylic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, thermogravimetric (TG) analysis, and single-crystal X-ray diffraction. Compounds 1−3 crystallize in the monoclinic system, space group C2/c. Compounds 1 and 2 are isostructural and exhibit novel 3D coordination frameworks constructed from two-dimensional (2D) wavelike lanthanide carboxylate layers and Ag(inic)4 complexes. To the best of our knowledge, they represent the first examples of 3D 4d−4f heterometallic coordination frameworks, in which the transition metal complexes bond to a 3D lanthanide carboxylate supramolecular framework with nanometer-sized channels built up from 2D wavelike layers. Compound 3 possesses an unusual 3D framework based on linkage of neodymium−carboxylate chains and silver(I) centers by inic ligands. The difference between both kinds of frameworks can be ascribed to the geometry effect of benzenedicarboxylate. Furthermore, the luminescent properties of 2 were studied.

Synthesis and crystal structure of a novel two-dimensional 3d–4f heterometallic coordination polymer constructed from three-ply-like layers

One novel 3d–4f heterometallic coordination polymer {[ZnPr 2(Dinic) 4(H 2O) 8] · H 2O} n ( 1) has been synthesized by hydrothermal method, where Dinic = 2,5-pyridinedicarboxylate. X-ray crystallography reveals that complex 1 possesses an interesting two-dimensional topology structure constructed from three-ply-like layers.

Heterometallic two-dimensional polymer containing cyanide-bridged praseodymium(III) and transition metals

A heterometallic cyanide-bridged 3d–4f heterometallic coordination polymer [Pr(DMF)4(H2O)3.5Fe(CN)6]·H2O (DMF = N,N′-dimethylformamide) has been synthesized and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group P2(1)/n with cell parameters: a = 17.669(5) A3, b = 8.927(3) A3, c = 19.967(6) A3, β = 95.807(5)°, V = 3133.2(16) A3, Z = 4. Multiple hydrogen bonds extend the dinuclear units into a novel 2-D topological architecture of an irregular triangular lattice of iron and praseodymium ions. The magnetic properties have been investigated.

Construction of 3d–4f heterometallic coordination polymers by simultaneous use of hexacyanometalate building-blocks and exo-bidentate ligands

The reaction of Pr(NO3)3·6H2O with 4,4′-bipyridine N,N′-dioxide (L) and K3[M(CN)6] [M = FeIII, CoIII] gives isomorphous heteropolynuclear complexes with formula [{(H2O)5LPr–NC–M(CN)5 }(μ-L)]·0.5L·4H2O, which exhibit a novel supramolecular architecture created by the interplay of coordinative, hydrogen bonding and π–π stacking interactions.