3d-4f Heterometallic Coordination Polymers Research Articles

Syntheses, structures and luminescence of a series of 4d–4f heterometallic coordination polymers constructed by 4,4′-oxybis(benzoicacid)

A series of Ln(III)-Ag(I) 4d–4f heterometallic coordination polymers [LnAg(oba) 2 (H 2 O)] n (Ln = Dy 1 , Ho 2 , Er 3 ) have been synthesized under hydrothermal reactions of 4,4′-oxybis(benzoicacid) (H 2 oba) with Ln(NO 3 ) 3 · 6H 2 O and AgNO 3 at 180 °C. All complexes are isostructural with 3D networks expanded from 1D zigzag chains and 2D layers. In addition, the luminescent property of compound 1 was investigated in the solid-state at room temperature. The coordination mode of H 2 oba ligand. • A series of Ln(III)-Ag(I) 4d-4f heterometallic polymers have been synthesized. • They are the first 4d-4f heterometallic polymers built by 4,4’- oxybis (benzoicacid). • The luminescent property of polymer 1 was investigated in the solid-state.

Two new 2p–3d–4f heterometallic coordination polymers based on 3,5-pyrazoledicarboxylic acid: synthesis, crystal structures and magnetic properties

Abstract Two new 2p–3d–4f heterometallic coordination polymers, [NaCuGd(pdc)2(H2O)7 ∙ 2H2O]n (1) and [NaCuEu(pdc)2(H2O)7 ∙ 2H2O]n (2), have been synthesized based on 3,5-pyrazoledicarboxylic acid (H3pdc). Single-crystal X-ray diffraction analysis reveals that complexes 1−2 are isostructural and both of them display an infinite two-dimensional brickwall-like layer structure consisting of three metal ions and bridged pyrazoledicarboxylate ligands. Magnetic properties of the complexes have been investigated in detail. Furthermore, free-ion approximation was used to fit the magnetic data and a good theory-experiment agreement was obtained for both 1 and 2.

Six new 3d–4f heterometallic coordination polymers constructed from pyrazole-bridged CuIILnIII dinuclear units

Reactions of lanthanide chlorides, copper hydroxycarbonate and 3,5-pyrazole dicarboxylic acid (H3pdc) under hydrothermal conditions result in six new 3d-4f heterometallic coordination polymers with two types of structures. Compounds [CuLn2(pdc)2(Hpdc)(H2O)4]·2H2O (Ln = Tb (1), Dy (2), Er (3), and Y (4) exhibit a layered porous structure, made up of Cu(II)Ln(III) di-nuclear units which are connected by protonated Hpdc(2-) ligand, while the others [Cu3Ln4(pdc)6(H2O)8] (Ln = Eu (5), Gd (6)) display a three-dimensional (3-D) framework structure, in which six Cu(II)Ln(III) di-nuclear units are cross-linked by two coordinated lanthanide atoms. The catalytic properties of 3 are investigated showing its activity and recyclability in the reaction of cyclopropanation of styrene.

Synthesis and structural characterization of 3d–4f heterometallic coordination polymers: from cluster to chain

Two new 3d–4f heterometallic coordination polymers, [MnIV2CeIV3O6Na(OAc)8(H2O)5](OH)·10H2O (1) and [MnIINdIII2Na2(OAc)8(H2O)6]·2(OH) (2) (OAc− = acetate), have been conventionally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. In 1, three Ce4+ and two Mn4+ cations are bridged by OAc− and μ3-O2− bridges forming a pentanuclear 3d–4f heterometallic [MnIV2CeIV3O6(OAc)8(H2O)5] cluster, while in 2, two Nd3+ and one Mn2+ cations are linked by carboxylic bridge of OAc− anions giving a 1D 3d–4f heterometallic [MnIINdIII2(OAc)8(H2O)6] chain. Additionally, pentanuclear heterometallic [MnIV2CeIV3O6(OAc)8(H2O)5] clusters in 1 are further connected by Na+ cations to result in a 1D chain, whereas the 3d–4f heterometallic chains in 2 are linked by Na1–O–Na1 dimers into a 2D array. Moreover, the variable magnetic susceptibilities of 1 and 2 are investigated.

3d–4f Heterometallic coordination polymers constructed by tetranuclear lanthanide-based cluster as secondary building unit

Four novel 3d–4f heterometallic coordination polymers [Dy4Mn(PDA)6(SO4)2 (H2O)4]·13H2O (1) and [Ln4M(PDA)4(SO4)2(INA)2(H2O)8]·5H2O [Ln = Gd, M = Mn (2); Ln = Eu, M = Zn (3); Ln = Tb, M = Zn (4); PDA = pyridine-2,6-dicarboxylate; INA = isonicotinate] have been hydrothermally synthesized and structurally characterized. Compound 1 possesses a 1D chainlike structure with the tetranuclear [Dy4(PDA)6(SO4)2(H2O)2] “metalloligand” linking the adjacent Mn atoms. Compounds 2–4 are isostructural and possess a 2D heterometallic layer network with a (4,4) connected topology. Furthermore, the magnetic and luminescent properties of compounds 1–4 were investigated.

Series of novel 3D microporous heterometallic 3d–4f coordination frameworks with (5,6)-connected topology: synthesis, crystal structure and magnetic properties

The hydrothermal reaction of rare earth nitrates, CuCN, 1H-1,2,3-triazole-4,5-dicarboxylic acid (H3tda), and isonicotinic acid (Hina) resulted in the formation of a new series of 3d–4f heterometallic coordination polymers [LnCu(tda)(ina)2(H2O)]·3H2O (Ln = Eu (1), Tb (2), Gd (3), Dy (4), Ho (5)], H3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Hina = isonicotinic acid). Complexes 1–5 are isostructural and structurally characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis reveals that the metal cations in these compounds are firstly interconnected by H3tda ligands to produce a carpet-shaped heterometallic ring [Ln2(tda)2Cu4], and then pillared by bridging Hina molecules to form the 3D layer-pillared porous Ln(III)–Cu(II) heterometallic coordination polymers. In addition, the magnetic properties of 1–5 were also investigated in detail.

A new family of 3d–4f heterometallic coordination polymers assembled with 1H-1,2,3-triazole-4,5-dicarboxylic acid: syntheses, structures and magnetic properties

Five isostructural copper(II)–lanthanide(III) heterometallic coordination polymers (CPs), {[Cu2Ln(TDA)2Cl(H2O)4]·2H2O}n [Ln = Gd (Cu–Gd), Tb (Cu–Tb), Dy (Cu–Dy), Ho (Cu–Ho) and Er (Cu–Er)] (H3TDA = 1H-1,2,3-triazole-4,5-dicarboxylic acid), have been synthesized under solvothermal conditions and structurally characterized in detail. In these CPs, two neighboring Cu(II) ions are connected via one μ2-Cl to form [Cu2Cl]3+ units, which are further linked into a copper chain through bridging TDA3−. The neighboring copper chains are further connected by lanthanide to form a two-dimensional structure with sql topology. The magnetic properties of the five isostructural heterometallic CPs have been studied as well.

Three 3d–4f heterometallic coordination polymers based on polydentate ligand and sulfate: Synthesis, crystal structure and photoluminescent properties

Abstract Three heterometallic coordination polymers [Gd 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 1 ), [Eu 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 2 ), and [Dy 2 Cu(Hbidc) 2 (SO 4 ) 2 (H 2 O) 7 ] n ( 3 ) (H 3 bidc = 1 H -benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions. They are characterized by elemental analysis (EA), infrared (IR) spectroscopy, thermogravimetric analysis (TGA), single crystal X-ray diffraction, and power X-ray diffraction (XRD). The results reveal that all complexes present almost identical three-dimensional (3D) PtS topology framework structures. The photoluminescent properties of 2 and 3 are investigated.

Copper(II)–lanthanide(III) coordination polymers constructed from pyridine-2,5-dicarboxylic acid: Preparation, crystal structure and photoluminescence

A series of 3d–4f heterometallic coordination polymers, formulated as {[Cu3Ln2(pydc)6(H2O)12]·4H2O}n [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {[CuNd2(pydc)4(H2O)3]·H2O}n (6) and {[Cu3Pr2(pydc)6(H2O)13]·4H2O}n (7) (where H2pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H2pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1–5 are isomorphous and present a two-dimensional network constructed from Ln2Cu2L2(H2O)2 SBU rings and CuL2(H2O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL2O2 units are assembled by H2pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc2− ligand is observed. The results indicate that the coordination flexibility of the pydc2− ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1–2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied.

Three-Dimensional Pillared-Layer 3d-4f Heterometallic Coordination Polymers With or Without Halides

Hydrothermal reactions of isonicotinic acid (Hina) and hemimellitic acid (H3hma) with lanthanide oxides and copper halides yielded 10 three-dimensional (3D) pillared-layer 3d-4f heterometallic coordination polymers (HCPs) with three structural types. They are formulated as [Ln2Cu2(μ2-X)(hma)(ina)4(H2O)2]n·2nH2O [Ln = La, X = Cl (I-A), Ln = La, X = Br (I-B), Ln = La, X = I (I-C), Ln = Nd, X = Cl (I-D), Ln = Nd, X = Br (I-E)], [Ln3Cu4.5I3.5(μ3-OH)(hma)(ina)6(H2O)]n·nH2O [Ln = Pr (II-A), Nd(II-B)], and [LnCu0.5(hma)(ina)(H2O)]n·nH2O [Ln = La (III-A), Ce (III-B), Pr (III-C)]. All the HCPs are characterized by single-crystal X-ray diffractions. In type I structures, Ln-organic layers are pillared by halide-bridged dinuclear [Cu2(μ2-Cl)(ina)4] units through Ln–O bonds. In type II structures, Ln-organic layers are pillared by two different kinds of monovalent Cu-based building units, namely, halide-free [Cu(ina)2] and halide-containing [Cu8(μ3-I)6(μ4-I)(ina)10]n. In type III structures, undulate heterometallic Cu(II)–Ln(III) layers are pillared by organic ina ligands via Ln–O and Cu–N bonds. The solid-state photoluminescent properties of I-D and II-B were also investigated at room temperature.

Syntheses, crystal structures and physical properties of two unusual 4d–4f heterometallic coordination polymers

Two novel heterometallic coordination polymers, [AgSm(pydc)2]·2H2O (1) and [AgTb(pydc)2]2·H2O (2) (H2pydc=pyridine-3,4-dicarboxylic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complexes 1 and 2 are isomorphous and exhibit 3D open framework heterometallic coordination polymer containing 1D channels occupied by lattice water molecules. To our knowledge, both compounds represent the rare examples of 3D open-framework 4d–4f heterometallic coordination polymers with open framework structure. Moreover, their luminescent and magnetic properties have also been investigated.

A novel two-dimensional 3d–4f heterometallic coordination polymer with (4, 4)-connected topology: Crystal structure, luminescence and magnetic properties

Abstract A novel 3d–4f heterometallic coordination polymer, namely, {[Sm2(PBDA)2·2H2O][Zn2(PBDA)2(Cl)2]}n (1), (H2PBDA = 3 -(pyridin-3-yl-oxy) benzene − 1,2-dicarboxylic acid) has been hydrothermally synthesized by using samarium(III) nitrate, H2PBDA acid and zinc chloride as raw materials, and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. Polymer 1 possesses two-dimensional (2D) network containing the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Variable temperature magnetic susceptibility studies reveal that 1 displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions, and the photoluminescent properties of polymer 1 as well as free H2PBDA ligand were also investigated.

Synthesis and structural characterization of a novel two-dimensional 3d-4f heterometallic coordination framework based on pentanuclear lanthanide cluster

A novel 3d-4f heterometallic coordination polymer, {[Tm5(μ3-OH)2(BDC)6(IN)2Cu(H2O)2]·(H2O)3}n (1) [BDC = benzene-1,2-dicarboxylate, IN = isonicotinate], has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. The compound crystallizes in monoclinic system, space group P21/c (No. 14), a = 13.7302(5) Å, b = 23.5428(3) Å, c = 21.5789(2) Å, β = 91.491(3)°, V = 6973.0(3) Å3, and Z = 4. The structure exhibits unusual two-dimensional Tm-carboxylate layer, which is constructed from the expansion of novel pentanuclear {Tm5} clusters. More interestingly, the heterometallic Cu(I) ions were successfully planted into such Ln-carboxylate layer by the bifunctional IN bridging ligands, resulting in the formation of an unprecedented 2D heterometallic lanthanide-transition-metal framework.

A family of three-dimensional 3d–4f and 4d–4f heterometallic coordination polymers based on mixed isonicotinate and 2-sulfobenzoate ligands: syntheses, structures and photoluminescent properties

Hydrothermal reactions of isonicotinic acid (Hina), 2-sulfobenzoic acid (H(2)sba), d-block metal salts and lanthanide oxides/hydroxides yielded 17 three-dimensional (3D) 3d-4f and 4d-4f heterometallic coordination polymers (HCPs). They are formulated as [LaAg(sba)(ina)(2)](n) (1), [Ln(2)Ag(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10)] and [Ln(2)Cu(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = La (11), Pr (12), Nd (13), Sm (14), Eu (15), Gd (16), Tb (17)]. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (XRD), infrared (IR) spectroscopy, elemental analysis (EA), and thermogravimetric analysis (TGA). It reveals that they represent two structural types of 3D HCPs. Furthermore, the investigations of their solid-state photoluminescent (PL) property demonstrate the extraordinary emission behaviors. HCP 1(La-Ag) exhibits tunable blue-to-green PL emissions by variation of excitation light. HCPs 6(Gd-Ag), 11(La-Cu), 12(Pr-Cu) and 16(Gd-Cu) show d(10)-metal-based ligand-to-metal charge transfer (LMCT) or metal-to-ligand charge transfer (MLCT) emissions. HCPs 3(Nd-Ag), 4(Sm-Ag), 5(Eu-Ag), 7(Tb-Ag), 8(Dy-Ag), 13(Nd-Cu), 14(Sm-Cu), 15(Eu-Cu) and 17(Tb-Cu) display characteristic PL emissions of the corresponding Ln(III) ions, while both d(10)-metal-based and 4f-metal-centered emissions are observed in the emission spectra of 4(Sm-Ag), 8(Dy-Ag), 14(Sm-Cu) and 17(Tb-Cu).

A series of 3d–4f heterometallic coordination polymers constructed from size-tunable copper halide clusters and lanthanide-organic motifs

A series of three-dimensional (3D) lanthanide–copper coordination polymers, namely [Ln2(NA)6Cu6Br6(H2O)4]·3.5H2O] [Ln = Sm (1), Eu (2), Tb (3), NA− = nicotinate], [Ln(NA)2Cu2Br2(C2O4)0.5(H2O)2]·2H2O [Ln = Gd (4), Er (5), C2O4 = oxalate], [Ln(NA)2Cu3Br3(OAc)(H2O)] [Ln = Sm (6), Eu (7), Tb (8), OAc = acetate], [Er2(NA)6Cu7Br7(H2O)4]·2H2O (9) and [Gd(NA)3Cu3Cl3(H2O)2]·H2O (10) have been hydrothermally synthesized and structurally characterized. Compounds 1–3 are constructed from Ln–organic chains and two distinct Cu4Br4 clusters possessing a (411.64)2(414.67)2(418.610)(49.6)2 topology. Compounds 4 and 5 are composed of two-dimensional (2D) Ln–organic layers and cubane-like Cu4Br4 clusters possessing a (43.66.8)(43)(46.66.83) topology. Compounds 6–8 can be viewed as the connection between Ln–organic chains and prism-like Cu6Br6 clusters with 4,6T50 topology. Compound 9 is constructed by Er–organic chains and dicubane-like Cu8Br7 clusters possessing a fluorite (flu) topology. Compound 10 consists of Gd–organic chains and inorganic Cu3Cl3 chains with tcj/hc topology. The diversity of the products demonstrates that the auxiliary ligand, pH value, reaction temperature and anion have significant effect on the construction of the structures. Moreover, the photoluminescence of 1–3 and 6–8, and the magnetism of 9 and 10 were investigated.

Two novel 3D 3d–4f polymers with 5-(isonicotinamido)isophthalic acid: Synthesis, structures and properties

Two new 3d–4f heterometallic coordination polymers [Mn0.5Ln(INAIP)2(H2O)2]·2H2O [Ln=Eu (1), Gd (2)] have been prepared by hydrothermal reactions of the corresponding lanthanide salt with 5-(isonicotinamido)isophthalic acid (H2INAIP) in the presence of MnCO3 and NaOH. Both complexes have been characterized by single crystal X-ray diffraction analyses, elemental analyses, infrared absorption spectra, and thermogravimetric analyses. The results of structural analyses show that 1 and 2 are isostructural and feature non-interpenetrated 3D coordination framework containing 2D (4,4) lanthanide–carboxylate layers. They have the same 3D structure with trinodal (3,3,4)-connected new topology net with Point (Schläfli) symbol (83)4(84·102)(86)2. In addition, photoluminescence and magnetic properties were also investigated.

An unusual 3D 3d–4f heterometallic coordination polymer based on the linkages of Sm2(IN)6 pillars and 2D [Cu7Br6]n+ layers: Crystal structure and luminescent property

Abstract An unusual three-dimensional (3D) pillared-layer 3d–4f (Cu+–Sm3+) heterometallic coordination polymer, {Sm2Cu7Br6(IN)7(H2O)5·3H2O}n (1) (HIN = isonicotinic acid), has been successfully synthesized by hydrothermal reaction of Sm2O3, CuBr2, HIN, HClO4 and H2O, and characterized by elemental analyses, IR, PXRD, and single-crystal X-ray diffraction. The structure determination reveals that 1 possesses 3D heterometallic framework constructed upon unprecedented [Cu7Br6]nn+ inorganic layers linked by dimeric Sm2(IN)6 pillars. Additionally, the thermogravimetric analysis and luminescent property of 1 were investigated and discussed.

Synthesis, crystal structure, and magnetic properties of two 3d–4f heterometallic coordination polymers

Two new 4f–3d heterometallic coordination polymers, [Gd 2 IIICo II(pydc) 3(ox)(H 2O) 4)·2H 2O] ( 1) and [Dy IIICu II(pydc) 2(ox) 1/2(H 2O) 2·H 2O] ( 2) (pydc = pyridine-2,5-dicarboxylate anion, ox = oxalate dianion) were successfully synthesized under hydrothermal condition. Structure and magnetism of the two coordination polymers were characterized by single crystal X-ray diffraction and Quantum Design (MPMS) SQUID magnetometer. In both compounds, metal centers were connected by double ligand bridges. In 1 the gadolinium ions were linked in sheets by O C O ligand bridges and these sheets were connected by separated cobalt coordination spheres to generate the overall 2-D structure. In 2 the dysprosium centers were constructed into one dimensional chain by O C O bridges from pydc ligand bridges and these chains were linked by oxalate bridges to form sheets and different sheets were connected by copper coordination planes. The copper centers in 2 were linked in chain by elongated O C O brides and the chains were connected by hydrogen bond to generate 3-D structure. Magnetic properties of the two complexes were investigated by variable temperature magnetic susceptibility. The magnetic data suggest that overall antiferromagnetic interactions are present in the two compounds.

Solvothermal synthesis, structure and properties of a new 3-D Cu(I)–Gd(III) heterometallic coordination framework

Abstract A new 3d–4f heterometallic coordination polymer, [CuGd2(INAIP)3(HCOO)(H2O)3]·3H2O (1), [H2INAIP = 5-(isonicotinamido)isophthalic acid] has been synthesized and characterized by single crystal X-ray diffraction analysis. The results of structural analyses show that 1 has a two-fold interpenetrated 3D coordination framework with a rare sqc27 topology. In addition, thermogravimetric and magnetic properties were also investigated.

2D pillar-chained 3d-4f heterometallic coordination polymers based on 2,4′-biphenyldicarboxylate

Abstract Two new 2D 3d-4f heterometallic compounds [LnIIICuII(2,4′-bpdc)2(μ3-OH)(C2H5OH)H2O]n (Ln = Tb(1) and Eu(2), 2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) have been successfully constructed by the solvothermal reaction of Ln2O3, Cu(NO3)2 and 2,4′-H2bpdc in ethanol, and characterized by element analysis, IR spectroscopy, and thermal analysis, as well as single crystal X-ray diffraction. The results reveal that two complexes are isomorphous and exhibit 2D pillar-chained coordination frameworks with 36·46·53 topology constructed from one-dimensional lanthanide-transition oxo-bridged heterometallic chains [LnCu(μ2-O)2(μ3-OH)2]n and (2,4′-bpdc2−)2 pillars. Furthermore, the photoluminescent properties of two compounds 1 and 2 were also studied.