3d-4f Coordination Research Articles

Anion-Induced Structural Diversity and Optical Chromism in a Series of Cyano-Bridged Heterometallic 3d-4f Coordination Polymers.

The self-assembly reaction of the neutral dicyano-bis(1,10-phenanthroline) iron(II) complex with lanthanide ions (Ln = Eu(III), Gd(III), Er(III)) provided two different classes of heterometallic cyano-bridged 3d-4f architectures depending on the nature of the counteranion, irrespective of the size of the 4f metal ion. Tetranuclear oligomers with a squared Fe2Ln2 core were isolated when using nitrate salts, whereas unusual 1D polymeric chains were obtained when resorting to triflate salts under the same synthetic conditions. It is shown that the different structural motifs have a remarkable impact on the thermal stability and the optical properties of the compounds, which display a notable optical ipsochromism of the parent Fe(II) complex upon coordination with the Ln ion. This effect is significantly more pronounced in the polymeric chain than in the Fe2Ln2 oligomer both in solution and in the solid state. Structural evidence suggests that this behavior is likely related to the geometry of the CN-Ln bridge. On the other hand, more extended π-stacking interactions in the oligomer give rise to a broad charge-transfer absorption (600-1500 nm), making this compound promising as NIR absorber. Density Functional Theory calculations and electrochemical studies demonstrate that the observed negative chromism originates from the stabilization of a mixed metal/cyanide character HOMO with respect to a phenanthroline-centered LUMO.

Heterobimetallic three-dimensional 4d-4f coordination polymers based on 5-methyl-1-(pyridyn-4-ylmethyl)-1H-1,2,3-triazole-3,4-dicarboxylate

Three novel 4f-4d heterometallic coordination polymers (CPs), [Ln(H2O)3CdL2(NO3)]·6H2O (L ​= ​ethyl 5-methyl-1-(pyridin-4-ylmethyl)-1H-1,2,3-triazole-3,4-dicarboxylate; Ln ​= ​Eu, Gd, Tb 1, 2 and 3, respectively) have been successfully synthesized by hydrothermal treatment and slow cooling-down crystallization. These CPs have been structurally characterized by single-crystal X-ray diffraction. 1–3 are isostructural and consist of a three-dimensional network showing channels. The networks are reinforced via hydrogen bonds and π-π stacking interactions. The crystal topology analysis shows an infinite 2D layer topology with net symbol {4,4} (sql). The magnetic behavior of these compounds is explained by the expected contribution of almost isolated Ln (III) ions. An energy gap of 375 ​cm−1 between the 7F0 ground state and the first excited state of compound 1 has been deduced from magnetic data showing an excellent agreement with the spectroscopic data.

Generalized Heisenberg-Type Magnetic Phenomena in Coordination Polymers with Nickel–Lanthanide Dinuclear Units

A new family of 3d–4f coordination polymers with the molecular formula [NiIILnIII(L)(dca)2(NO3)]n [Ln = Eu (1), Gd (2), Tb (3), Dy (4), and Ho (5); H2L = N,N′-bis(2-hydroxy-3-methoxy-5-methylbenzyl)homopiperazine; dca = dicyanamide] has been synthesized in search for new single-molecule magnet (SMM) materials containing highly anisotropic lanthanides. The magnetic properties of these materials have been established by DC and AC magnetometry and explained quantitatively by comprehensive phenomenological modeling based on a generalized Heisenberg-type model, hypothesized previously based on first-principles calculations. Single-crystal X-ray diffraction has shown that the compounds are isostructural, with lanthanide atoms occupying a nine-coordination site with muffin-like geometry and individual NiII–LnIII units linked by dca anions. Other than the paramagnetic compound 1, 2–5 exhibit intra-unit ferromagnetic 3d–4f interactions, favorable for a large spin ground state. A slow field-induced relaxation of magnetization has been observed in compound 4 (only), displaying a substantial energy barrier of Ueff/kB = 26.2(5) K, below 6 K. This is attributed to an easy-plane anisotropy and is consistent with the relaxation in systems with a Kramers ground state doublet and hyperfine interactions.

Linear shaped hetero-metallic [Zn2Ln4] clusters with Schiff base ligand: Synthesis, characterization and magnetic properties

A series of isostructural 3d–4f coordination clusters (CCs) [Zn2Ln4(L1)4(L2)2(OAc)2(N3)2] [Na2(OH2)2(NO3)3.2(N3)0.8]∙2MeCN, where Ln = Dy (1), Ho (2), Er (3), Tm (4), and Yb (5), L1 = 6-Methoxy-2-(2-pyridylmethyliminomethyl)phenol and L2 = (E)-2-methoxy-6-(2-((3-methoxy-2-oxidobenzylidene)amino)-1-oxido-2-(pyridin-2-yl)ethyl)phenolate has been synthesised and structurally characterised. The magnetic properties of 1–5 have been investigated using dc and ac susceptibility measurements. The paramagnetic metal ions within the clusters are weakly antiferromagnetically coupled, with the Er and Dy compounds displaying slow relaxation of their magnetisation. This is the first report of this versatile ligand being used to target 3d–4f coordination clusters.

New Cyanido-Bridged Heterometallic 3d-4f 1D Coordination Polymers: Synthesis, Crystal Structures and Magnetic Properties

Three new 1D cyanido-bridged 3d-4f coordination polymers, {[Gd(L)(H2O)2Fe(CN)6]·H2O}n (1GdFe), {[Dy(L)(H2O)2Fe(CN)6]·3H2O}n (2DyFe), and {[Dy(L)(H2O)2Co(CN)6]·H2O}n (3DyCo), were assembled following the building-block approach (L = pentadentate bis-semicarbazone ligand resulting from the condensation reaction between 2,6-diacetyl-pyridine and semicarbazide). The crystal structures consist of crenel-like LnIII-MIII alternate chains, with the LnIII ions connected by the hexacyanido metalloligands through two cis cyanido groups. The magnetic properties of the three complexes have been investigated. Field-induced slow relaxation of the magnetization was observed for compounds 2DyFe and 3DyCo. Compound 3DyCo is a new example of chain of Single Ion Magnets.

Insights into nature of a magnetization plateau of 3d-4f coordination polymer [Dy2Cu2]n from a spin-1/2 Ising-Heisenberg orthogonal-dimer chain

The ground state and magnetization process of an exactly solved spin-1/2 Ising-Heisenberg orthogonal-dimer chain with two different gyromagnetic factors of the Ising and Heisenberg spins are investigated in detail. It is shown that the investigated quantum spin chain exhibits up to seven possible ground states depending on a mutual interplay of the magnetic field, intra- and inter-dimer coupling constants. More specifically, the frustrated and modulated quantum antiferromagnetic phases are responsible in zero-temperature magnetization curves for a zero magnetization plateau. The intermediate 1/11- and 5/11-plateaus emerge due to the frustrated and modulated quantum ferrimagnetic phases, while the intermediate 9/11- and 10/11-plateaus can be attributed to the quantum and classical ferrimagnetic phases. It is conjectured that the magnetization plateau experimentally observed in a high-field magnetization curve of 3d-4f heterobimetallic coordination polymer [{Dy(hfac)2(CH3OH)}2{Cu(dmg)(Hdmg)}2]n (H2dmg = dimethylglyoxime; Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) could be attributed to the classical and quantum ferrimagnetic phases.

Heterometallic (3d-4f) Coordination Clusters with Unique Topology: Self-Assembly Synthesis, Structural Features, and Magnetic Properties

Three heterometallic Fe6Ln4 clusters were self-assembled by using N-methyldiethanolamine (H2mdea) and 3,5-dinitrobenzoic acid (Hdnbz) as principal building blocks ...

Synthesis and characterization of two isostructural 3d-4f coordination compounds based on pyridine-2,6-dicarboxylic acid and 4,4'-bipyridine.

The design and synthesis of 3d-4f heterometallic coordination polymers have attracted much interest due to the intriguing diversity of their architectures and topologies. Pyridine-2,6-dicarboxylic acid (H2pydc) has a versatile coordination mode and has been used to construct multinuclear and heterometallic compounds. Two isostructural centrosymmetric 3d-4f coordination compounds constructed from pyridine-2,6-dicarboxylic acid and 4,4'-bipyridine (bpy), namely 4,4'-bipyridine-1,1'-diium diaquabis(μ2-pyridine-2,6-dicarboxylato)tetrakis(pyridine-2,6-dicarboxylato)bis[4-(pyridin-4-yl)pyridinium]cobalt(II)dieuropium(III) octahydrate, (C10H10N2)[CoEu2(C10H9N2)2(C7H3NO4)6(H2O)2]·8H2O, (I), and 4,4'-bipyridine-1,1'-diium diaquabis(μ2-pyridine-2,6-dicarboxylato)tetrakis(pyridine-2,6-dicarboxylato)bis[4-(pyridin-4-yl)pyridinium]cobalt(II)diterbium(III) octahydrate, (C10H10N2)[CoTb2(C10H9N2)2(C7H3NO4)6(H2O)2]·8H2O, (II), were synthesized under hydrothermal conditions and characterized by IR and fluorescence spectroscopy, thermogravimetric analysis and powder X-ray diffraction. Both compounds crystallize in the triclinic space group P-1. The EuIII and TbIII cations adopt nine-coordinated distorted tricapped trigonal-prismatic geometries bridged by three pydc2- ligands. The CoII cation has a six-coordination environment formed by two pydc2- ligands, two bpy ligands and two coordinated water molecules. Adjacent molecules are connected by π-π stacking interactions to form a one-dimensional chain, which is further extended into a three-dimensional supramolecular network by multipoint hydrogen bonds.

Assembly of a New 2D Heterometallic 3d–4f Coordination Polymer Bearing Planar Tetranuclear Square Building Blocks

A new two-dimensional (2D) 3d–4f heterometallic coordination polymer, which is {[Tb2Zn4(µ3-TFMIDC)4(µ4-HTFMIDC)(H2O)8]·2H2O}n, has been successfully synthesized by the solvothermal reaction of 2-(trifluoromethyl)-1H-4,5-imidazole dicarboxylic acid (H3TFMIDC) with Zn(II) and Tb(III) ions. The title compound was structurally characterized by diverse characterization techniques including single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Single-crystal structure analysis reveals that the as-preprared compound is a 2D heterometallic 3d–4f coordination network based on interesting planar tetranuclear squares [Zn4(TFMIDC)4] as building blocks, representing the first example of novel heterometallic coordination polymer based on the H3TFMIDC ligand. In addition, the title compound exhibits very intense green luminescence and characteristic transitions of the Tb(III) ion when excited at 291 nm. Lattice parameters for the title compound: a = 11.1449(12) A, b = 12.8498(13) A, c = 37.553(4) A, α = β = γ = 90°, V = 5378.0(10) A3, Z = 4. A unique 2D 3d–4f heterometallic coordination polymer containing interesting planar tetranuclear square building blocks has been constructed by the solvothermal reaction of 2-(trifluoromethyl)-1H-4,5-imidazole dicarboxylic acid (H3TFMIDC) with Zn(II) and Tb(III) ions.

Syntheses, Crystal Structures, and Fluorescence Properties of 3d–4f Coordination Polymers LnNi (Ln = Er, Eu)

Two novel 3d–4f coordination polymers [Ln(NiL)(Nipt)(C2O4)0.5 · H2O] · H2O (Ln = Er (I), Eu (II) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H2Nip = 5-nit-roisophthalic acid) were obtained by using 5-nitroisophthalate and mononuclear macrocyclic oxamide complex NiL as co-ligand to react with Ln(NO3)3 ⋅ 6H2O (Ln = Er, Eu) under solvothermal condition, and characterized by single crystal X-ray diffraction (CIF files CCDC nos. 1587618 (I) and 1587619 (II)). Two complexes are isostructural structure and exhibit a two-dimensional network architecture formed by [Ln(III)Ni(II)] units via the oxamide, 5-nitroisophthalate and oxalate bridges, and adjacent 2D structures are linked together with C–H⋅⋅⋅O and O–H⋅⋅⋅O intermolecular hydrogen bonds to form a 3D superamolecular architectures. The fluorescence properties of I and II are also characterized.

A Self-Assembled ZnII-NdIII Heterohexanuclear Dimer Based on a Hexadentate N₂O₄-Type Ligand and Terephthalic Acid: Synthesis, Structure, and Fluorescence Properties.

A self-assembled ZnII-NdIII heterohexanuclear coordination compound [Zn4Nd2(L)4(bdc)2]·2NO3 based on a hexadentate Salamo-like chelating ligand (H2L = 1,2-bis(3-methoxysalicylideneaminooxy)ethane]) and H2bdc (H2bdc = terephthalic acid) has been synthesized and characterized by elemental analyses, IR and UV/Vis spectra, and X-ray crystallography. Two crystallographically equivalent [Zn2Nd(L)2] moieties lie in the inversion center linked by two (bdc)2− ligands leading to a heterohexanuclear dimer in which the carboxylato group bridges the ZnII and NdIII atoms. The heteropolynuclear 3d-4f coordination compound includes four ZnII atoms, two NdIII atoms, four completely deprotonated (L)2− units, two fully deprotonated (bdc)2− units, and two crystalling nitrate ions. All of the ZnII atoms in the ZnII-NdIII coordination compound possess trigonal bipyramidal geometries and the NdIII atoms possess distorted bicapped square antiprism coordination arrangements. In addition, the fluorescence properties of the ligand and the ZnII-NdIII coordination compound were investigated.

Transformative 3d–4f coordination cluster carriers

The aim of this perspective is to summarise the use of the reported 3d-4f Coordination Clusters (CCs) in catalytic reactions and to demonstrate the potential of this emerging field. The pioneering work of Shibasaki, Matsunaga and others, demonstrated the use of 3d-4f in situ systems to catalyse asymmetric organic transformations. Our recent studies show that well characterised 3d-4f CCs catalyse numerous organic transformations and useful mechanistic aspects of their catalysis can be obtained. Furthermore, we have shown that by manipulation of the metal ion coordination environment; the nature of the 3d and lanthanide ions and the organic periphery of the ligand can all improve the efficacy of a 3d-4f CC catalyst. All in situ formed and well characterized 3d-4f CCs involved in catalysis are discussed.

Filling the Missing Links of M3n Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and Magnetic Properties of the Ni10Ln5 and the Er3n Wheels

In this paper, we proposed a number rule for 3d-4f and 4f cyclic coordination cages (CCCs); that is, CCCs consisting of vertex-sharing M4(μ3-OH)4 (M = 3d transition metal or 4f lanthanide ions) units should have 3 × n metal centers (abbreviated M3n), where n represents the number of the M4(μ3-OH)4 subunits. Under this number rule we reasoned that some species of CCCs, for example, the pentadecanuclear 3d-4f wheel and the pure 4f wheels with 9 or 18 centers, should practically have existed. However, there are no such complexes reported in the literature. To realize such CCCs we employed a mixed-ligand approach, that is, to simultaneously use the primary and the ancillary ligands for syntheses. This approach successfully leads to the isolation of two families of CCCs, namely, the Ni10Ln5 (Ln = Gd and Y) mixed-metal wheels and the Er3n (n = 4, 5, and 6) pure 4f metal wheels. These two families of CCCs unambiguously fill the missing links of the M3n prototype CCCs. Moreover, dominated ferromagnetic interaction indicates high ground-spin state for the Gd5Ni10 wheel. The ferromagnetic interactions between the nickel centers are verified using the diamagnetic Y(III) analogue, which reveals an averaged coupling constant (J = 2.7 cm-1), while accompanied by a large negative zero-field splitting parameter (D = -6.1 cm-1) for single Ni(II) ions. Interestingly, the Y(III)-diluted Er12 wheel shows slow magnetic relaxation behavior, presumably indicating the magnetically anisotropic nature of the erbium(III) ions.

Thermochromic properties of cucurbituril-based 3d-4f heterometallic material

One 3d-4f coordination compound was synthesized by reaction between cucurbit[6]uril samarium and copper chlorides with molecular formula [Sm2Cu2(C36H36N24O12)Cl10] (H2O)26. Upon heating, the compound undergoes a reversible colour change due to a solid-to-solid phase transition of the [CuCl4]2− anions. The powder diffraction and luminescence spectroscopy suggest small changes in the structure during the heating/cooling process.

SMM behaviour and magnetocaloric effect in heterometallic 3d-4f coordination clusters with high azide : metal ratios.

We present the synthesis and characterization of heterometallic compounds with a very large azide to metal ratio. Their interesting structures give rise to fascinating magnetic properties.

Two 3d-4f Heterometallic Coordination Polymers of Macrocyclic Oxamide with Benzotriazole-5-carboxylate Co-ligand: Syntheses, Crystal Structures and Magnetic Properties

Two heterometallic 3d–4f coordination polymers, [Gd(CuL)2(Hbtca)(btca)(H2O)]·2H2O (1) and [Er(CuL)2(Hbtca)(btca)(H2O)]·H2O·CH3OH (2) (CuL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H2btca = benzotriazole-5-carboxylic acid) were synthesized by solvothermal methods and characterized by single-crystal X-ray diffraction. Complexes 1 and 2 exhibit a double-strand meso-helical chain structures formed by [LnIIICuII2] (LnIII = Gd, Er) units by oxamide and benzotriazole-5-carboxylate bridges. They are isomorphic except that one free water molecule of 1 is replaced by a methanol molecule. All 1D chains are further interlinked by hydrogen bonds resulting in a 3D supramolecular architecture. The magnetic properties of the compound 1 and 2 are also discussed.

Seven 3d-4f coordination polymers of macrocyclic oxamide with polycarboxylates: Syntheses, crystal structures and magnetic properties

Seven new 3d–4f heterometallic coordination polymers, [Ln(CuL)2(Hbtca)(btca)(H2O)]·2H2O (Ln = TbIII1, PrIII2, SmIII3, EuIII4, YbIII5), [Nd(NiL)(nip)(Rnip)]·0·25H2O·0.25CH3OH (R= 0.6CH3, 0.4H) 6 and [Nd2(NiL)(nip)3(H2O)]·2H2O 7(CuL or NiL, H2L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H2btca = benzotriazole-5-carboxylic acid; H2nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1–5 exhibit a double-strand meso-helical chain structures formed by [LnIIICuII2] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits a four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip2− bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χMT versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6cm−1, zj’ = −0.33cm−1, gav = 1.94; for 5, Δ = 6.98cm−1, zj’ = 1.53cm−1, gav = 1.85).

Near-Infrared Photoluminescence in Hexacyanido-Bridged Nd–Cr Layered Ferromagnet

Hexacyanidochromate(III) anion is here explored as the building block for the construction of bimetallic 3d-4f coordination polymers that combine spin ordering and luminescence. We report the two-dimensional cyanido-bridged {[NdIII(pmmo)2(H2O)3][CrIII(CN)6]} (1) layered framework obtained by the spontaneous crystallization from the aqueous solution of Nd3+, pyrimidine N-oxide (pmmo), and [CrIII(CN)6]3–. 1 crystallizes as light green plates in the orthorhombic Pbca space group and reveals a topology of a square grid built of nine-coordinated [NdIII(μ-NC)4(H2O)3(pmmo)2]− complexes of a nearly capped square antiprism geometry, and six-coordinated octahedral [CrIII(CN)6]3– moieties. Because of the presence of cyanide-mediated ferromagnetic coupling between paramagnetic NdIII (J = 9/2) and CrIII (S = 3/2) centers, 1 exhibits a long-range ferromagnetic ordering below Curie temperature of 2.8 K, with a tiny magnetization-field hysteresis loop detected at 1.8 K. Under the UV light irradiation, 1 shows the near-in...

Two-dimensional 3d–4f coordination polymers based on compartment compounds: [NiLn(L)(NO3)2(4-pca)(H2O)] (Ln = Nd, Eu, Tb; H2L = 1,3-bis((3-methoxysalicylidene)amino)propane); 4-Hpca = pyridine-4-carboxylic acid)

This paper describes the preparation and properties of Ni–Nd, Ni–Eu, and Ni–Tb coordination polymers, by using dinuclear 3d–4f compartment compounds as secondary building units. Under microwave-heating conditions in acetonitrile, two-dimensional 3d–4f coordination polymers, [NiLn(L)(NO3)2(4-pca)(H2O)] {Ln=Nd (1), Eu (2), Tb (3)}, were prepared from [NiLn(L)(NO3)(CH3CN)(H2O)4](NO3)2(H2O) and pyridine-4-carboxylic acid (4-Hpca). X-ray diffraction studies of polymers 1 and 2 clearly revealed that the pyridine terminal of the compartment ligand (L) is coordinated to the d-block metal (Ni) and the carboxylate terminal is coordinated the f-block metal (Nd or Eu). Compounds 2 and 3 exhibited the emission quenching of the Ln3+ ion, which probably arises from the Ln3+→Ni2+ energy transfer.

Copper(i)–lanthanide(iii) heterometallic metal–organic frameworks constructed from 3-(3-pyridyl)acrylic acid: syntheses, structures, and properties

The first employment of 3-(3-pyridyl)acrylic acid (3-HPYA) in 3d–4f coordination chemistry is reported. Hydrothermal reactions of 3-HPYA with lanthanide oxides and copper halides led to the formation of 17 novel copper(I)–lanthanide(III) heterometallic coordination compounds with four structural types, namely, [Ln(3-PYA)3Cu3Cl3(H2O)2]·H2O [Ln = Dy (1), Eu (2), Gd (3), Tb (4)] (I), [Ln(3-PYA)3CuI(H2O)2]·0.5H2O [Ln = Dy (5), Gd (6), Tb (7), Sm (8)] (II), [Ln(3-PYA)3CuBr(H2O)2]·xH2O [Ln = La (9), Eu (10), x = 1; Sm (11), Nd (12), x = 0.5] (II), [LnCu2(3-PYA)2I2(ox)0.5(H2O)2]·(H2O)2 [Ln = Eu (13), Gd (14), Nd (15)] (III) and [LnCu2(3-PYA)2Br2(ox)0.5(H2O)]·(H2O) [Ln = Gd (16), Tb (17)] (IV) (ox = oxalate). These compounds were thoroughly characterized by single crystal and powder X-ray diffraction, as well as elemental analyses, FT-IR spectroscopy and thermal studies. All the compounds are constructed from halide-containing copper–inorganic motifs and Ln-containing motifs. Compounds of type I are constructed from 1D zigzag Dy–organic chains with [Cu6Cl6] ladder-like clusters, exhibiting a 2D binodal (5, 6)-connected topology. An unusual chemical rearrangement from [Cu6Cl6] to [Cu2Br2]/[Cu2I2] clusters occurs in the formation of type II structures. They are isostructural and exhibit a 3D coordination framework based on dinuclear [Dy2O2] subunits and [Cu2Br2]/[Cu2I2] clusters as nodes, possessing a binodal (4, 6)-connected net. In the type III structure, the Ln–organic motifs propagate along the b-axis, while the Cu–inorganic motifs propagate in the perpendicular direction along the a-axis, both of which are further interconnected to give unique 3D (3, 3, 4, 4, 6)-connected nets with {42·6}2{42·82·1010·12}{43·62·8}4{43}2 topologies. The type IV structure, based on structural analysis results, features a non-interpenetrated 3D coordination framework containing 2D Ln–organic layers and Cu2Br2 chains with a new 5-nodal (3, 3, 4, 4, 8)-connected topology net (point symbol: {42·6}2{43·63}4{43}2{46·610·810·102}). Our present work represents the first example of heterometallic Cu(I) halide–Ln(III)–organic frameworks utilizing 3-HPYA as an organic ligand. The diversity of the products demonstrates that the anion, pH value and reaction temperature have significant effects on the construction of the structures. Moreover, the photoluminescence properties of 2, 4, 7, 10, 12, 13, and 15 and the magnetic properties of 1, 5, and 16 were investigated.