钆-邻氟苯甲酸-邻菲咯啉配合物的合成、晶体结构

由于有机羧酸化合物具有多种配位方式,以此为配体的稀土羧酸配合物具有多种多样的晶体结构。这类配合物有单核分子、双核分子和高聚物,可形成1D、2D、3D等多种结构。而且由于这类配合物在萃取分离、催化和发光材料等方面的潜在应用一直受到学者们的广泛研究。稀土与苯甲酸及其衍生物和1,10-邻菲咯啉的混合配体配合物已有很多报道[1￣6]。文献[1,2]报道了在同一个配合物的结构单元中存在两个晶体学不等同的双核分子,是由于羧基桥联方式不同而导致的。其中一个分子的两个中心离子通过4个苯甲酸的羧基桥联,另一个只有2个羧基桥联。我们合成了…     

Synthesis,crystal structures,and characterization of copper(II) carboxylate complexes incorporating 1,10-phenanthroline and bipyridine

A series of Cu(II) carboxylate complexes (carboxylate?=?2-fluorobenzoic acid (2-HFBA) or 4-fluorobenzoic acid (4-HFBA)) containing either one chelating 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and thermal analyses. In [Cu(bipy)(H₂O)(2-FBA)₂] (1), [Cu(bipy)(H₂O)(4-FBA)₂] (3), and [Cu(phen)(H₂O)(2-FBA)₂] (4), Cu is five-coordinate in a square pyramidal geometry and four-coordinate in [Cu(phen)(2-FBA)₂] (2). The four complexes are extended into 1-D chains through hydrogen-bonding and π?···?π interactions in 1 and 4, only hydrogen-bonding in 2, and π?···?π interactions in 3. These contacts lead to aggregation and supramolecular self-assembly.     

Synthesis,crystal structure and luminescence of three europium complexes with 2-iodobenzoic acid

Three new complexes, [Eu(2-IBA)₃?·?H₂O] _n (1), [Eu(2-IBA)₃?·?2,2′-bpy]₂ (2), and [Eu(2-IBA)₃?·phen]₂ (3) (2-IBA?=?2-iodobenzoato; 2,2′-bpy?=?2,2’-bipyridine; phen?=?1,10-phenanthroline) were synthesized, and their crystal structures determined by X-ray diffraction. In complex 1, Eu³⁺ ions are linked through carboxylate groups via bridging – chelating – bridging coordination modes to form a one-dimensional polymeric chain. The carboxylate groups are tetradentate-bridged. Complex 2 is binuclear with an inversion center, in which europium is nine-coordinated with seven oxygen atoms from five 2-IBA ligands and two nitrogen atoms from one 2,2′-bpy molecule in a distorted monocapped square antiprism. The crystal structure of 3 is similar to that of 2. These complexes emit red light luminescence. The ⁵ D ₀?→?⁷ F _j (j?=?1–4) transition emission of Eu³⁺ ion has been observed.     

Hydrothermal synthesis and crystal structure of two new lanthanide coordination polymers with 1,2-phenylenediacetate

Two new compounds {[Ln₂(1,2-pda)₃(H₂O)₂]·?2H₂O} _n (1,2-H₂pda?=?1,2-phenylenediacetic acid, Ln?=?Tb, 1; Ho, 2) were prepared by hydrothermal reaction and characterized by X-ray crystallography. The Ln³⁺ is nine-coordinate by eight oxygen atoms of six 1,2-pda ligands and one oxygen of water. Ln³⁺ ions are bridged by 1,2-pda ligands via bridging/chelating-bridging pentadentate and chelating-bridging/chelating-bridging hexadentate coordination to form 3-D framework structures. Complex 1 emits strong green fluorescence corresponding to ⁵D₄???⁷F_j (j?=?6–3) transitions of the Tb³⁺.     

Synthesis and crystal structure of two praseodymium 2-iodobenzoic acid complexes

Two new complexes, {[Pr(2-IBA)₃?·?2,2′-bipy]₂·[Pr(2-IBA)₃?·?2,2′-bipy]₂?·?0.5C₂H₅OH?·?H₂O} (1) and [Pr(2-IBA)₃?·?phen]₂ (2) (2-IBA?=?2-iodobenzoate; 2,2′-bipy?=?2,2′-bipyridine; phen?=?1,10-phenanthroline) were synthesized, and their crystal structures were determined by X-ray diffraction. Complex 1 consists of two binuclear molecules [Pr(2-IBA)₃?·?2,2′-bipy]₂ (a) and [Pr(2-IBA)₃?·?2,2′-bipy]₂ (b), half uncoordinated ethanol and one uncoordinated water. In the two molecules (a) and (b), the coordination environment of central ions is similar. The Pr1³⁺ ion in molecule (a) and Pr2³⁺ ion in molecule (b) are nine-coordinate with seven oxygen atoms from five 2-IBA ligands and two nitrogen atoms from one 2,2′-bipy molecule. The crystal structure of complex 2 is similar to that of binuclear [Pr(2-IBA)₃?·?2,2′-bipy]₂ in complex 1.     

Synthesis,crystal structure and properties of three ternary dysprosium 2-halogenated benzoic acid complexes

Three ternary dysprosium complexes [Dy(2-ClBA)₃?·?phen]₂ (1), [Dy(2-ClBA)₃?·?2,2′-bipy]₂ (2), and [Dy(2-BrBA)₃?·?phen]₂ (3) (where 2-ClBAH?=?2-ClC₆H₄COOH, 2-BrBAH?= 2-BrC₆H₄COOH, phen?=?1,10-phenanthroline, and 2,2′-bipy?=?2,2′-bipyridine) have been synthesized and characterized by X-ray single crystal diffraction. Complex 1 consists of two independent binuclear molecules, [Dy(2-ClBA)₃?·?phen]₂ (a) and [Dy(2-ClBA)₃?·?phen]₂ (b), in which the coordination environment is similar. Each Dy³⁺ is nine coordinate with two nitrogens from phen and seven oxygens from five 2-ClBA groups. 2-ClBA groups coordinate to Dy³⁺ in three ways, bidentate chelating, bidentate-bridging and terdentate-bridging. Complexes 2 and 3 consist of one binuclear molecule. The crystal structure of 2 is similar to that of binuclear molecule (a) or (b) of complex 1. In 3, each Dy³⁺ ion is eight-coordinate by two nitrogens from phen and six oxygens from five 2-BrBA groups. 2-BrBA groups coordinate to the Dy³⁺ ion in two ways, bidentate chelating and bidentate-bridging. The complexes were studied by UV, DTA-TG, and fluorescence spectrometry.     

Hydrothermal syntheses,crystal structures and luminescence properties of two lanthanide dinuclear complexes with hexafluoroglutarate

Two complexes [Ln₂(hfga)₂(phen)₄(H₂O)₆] · hfga · 2H₂O (H₂hfga = hexafluoroglutaric acid, phen = 1, 10-phenanthroline, Ln=Tb, 1; Eu, 2) were synthesized under hydrothermal conditions and their structures determined by X-ray crystallography. The complexes consist of dinuclear units with an inversion center. Each Ln(III) is nine-coordinate with two carboxylate oxygens from two hfga ligands, three oxygens from water and four nitrogens from two phen molecules. Two carboxylate groups of one hfga adopt monodentate coordination to Ln(III) as a long bidentate bridge linking two Ln(III) ions to form a dimer. Ln(III) ··· Ln(III) distances of 9.027(3) Å for 1 and 9.043(3) Å for 2 were observed. Both complexes emit strong fluorescence and show characteristic emission of Tb(III) and Eu(III) ions, respectively.     

Hydrothermal syntheses and characterization of four 2-D lanthanide coordination polymers with glutarate and 1,10-phenanthroline

Four 2-D coordination polymers Ln₂(phen)₂(C₅H₆O₄)₃ [Ln?=?Pr(1), Eu(2), Er(3), Yb(4), phen?=?1,10-phenanthroline] were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data reveal that these complexes are isostructural. In the asymmetric unit, the two Ln(III) ions are nine-coordinate and have similar coordination environments. The Ln(III) ions are built into 2-D layers by three different coordination modes of glutarate. The resulting 2-D layer forms 3-D supramolecular architecture by two types of π···π stacking interactions. All the complexes were characterized by IR spectra and thermogravimetric analysis, and the emission spectrum shows that Eu₂(phen)₂(C₅H₆O₄)₃ possesses strong luminescence.     

Two cadmium(II) addition compounds with 3-hydroxy-2,7-naphthalenedisulfonate containing aromatic diamines and their 3-D net

{[CdCl(2,2′-bipy)₂(H₂O)]⁺·[Cd(3-O^?-2,7-NDS)(2,2′-bipy)₂]^?·3H₂O} (1) and {[Cd(phen)₃]²⁺·2[Cd(3-O^?-2,7-NDS)(phen)₂]^?·8.5H₂O} (2) (3-OH-2,7-NDS?=?3-hydroxy-2,7-naphthalenedisulfonate, phen?=?1,10-phenanthroline, and 2,2′-bipy?=?2,2′-bipydine) were prepared and characterized by X-ray single-crystal diffraction. Compound 1 contains a discrete coordination cation [CdCl(2,2′-bipy)₂(H₂O)]⁺ and a coordination anion [Cd(3-O^?-2,7-NDS)(2,2′-bipy)₂]^?; 2 contains a discrete coordination cation [Cd(phen)₃]²⁺ and two coordination anions [Cd(3-O^?-2,7-NDS)(phen)₂]^?. There are numerous weak interactions among the coordination cation, coordination anion, and free water molecules, such as O–H?···?O hydrogen bonds, π?···?π stacking, and Cl^??···?π interactions in 1 and π?···?π stacking and C–H?···?π interactions in 2. The cations and anions as building blocks are connected to construct different 3-D supramolecular architectures via weak intermolecular interactions. Particularly, the capsule structure of 1 was observed.     

Host–guest complexes of mixed glycol-phenanthroline cryptands: prediction of ion selectivity by quantum chemical calculations IV

Abstract Structures and complex-formation energies, calculated with DFT (B3LYP/LANL2DZp) for the cryptands [2.2.phen] and [2.phen.phen] with endohedrally complexed alkali and alkaline earth metal ions, were utilized to predict their ion selectivity. Both cryptands [2.2.phen] and [2.phen.phen] have a cavity size smaller than [2.2.2], [phen.phen.phen] and [bpy.bpy.bpy], and prefer to bind K⁺ and Sr²⁺, whereas [2.2.phen] that is larger than [2.phen.phen], has a preference for Ba²⁺, and [2.phen.phen] favours Na⁺ and Ca²⁺. The cryptand flexibility is mainly attributed to the presence of CH₂–N_SP3···N_SP3–CH₂ groups. Graphical abstract Host–Guest Complexes of mixed Glycol-Phenanthroline Cryptands—Prediction of Ion Selectivity by Quantum Chemical Calculations III Ralph Puchta* and Rudi van Eldik Keywords Cation selectivity Host–guest DFT DFT-studies allow a sensitive analysis of selectivity and cage size. Calculations predict a favourable binding of K⁺, Sr²⁺ and Ba²⁺ by [2.2.phen], and binding of K⁺, Na⁺, Ca²⁺ and Sr²⁺ by [2.phen.phen]. The cryptands fold around the ions by twisting their torsion angles in order to reach the best coordination mode for each cation. For “Prediction of ion selectivity by quantum chemical calculations III” see, R. Puchta, R. van Eldik. Aust. J. Chem. 60, 889–897 (2007).     

Hydroxo Bridged Dinuclear Rare Earth Complexes: Syntheses and Crystal Structures of [Ln2(phen)4(H2O)4(OH)2](NO3)4(phen)2 with Ln = Er,Lu

Reactions of phenanthroline (phen) and Er(NO₃)₃ · 5 H₂O or Lu(NO₃)₃ · H₂O in CH₃OH/H₂O yield [Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄(phen)₂ with Ln = Er ( 1 ), Lu ( 2 ). Both isostructural complex compounds crystallize in the triclinic space group P 1 (no. 2) with the cell dimensions: a = 11.257(2) Å, b = 11.467(2) Å, c = 14.069(2) Å, α = 93.93(2)°, β = 98.18(1)°, γ = 108.14(1)°, V = 1696.0(6) ų, Z = 1 for ( 1 ) and a = 11.251(1) Å, b = 11.476(1) Å, c = 14.019(1) Å, α = 93.83(1)°, β = 98.27(1)°, γ = 108.27(1)°, V = 1689.0(3) ų, Z = 1 for ( 2 ). The crystal structures consist of the hydroxo bridged dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cations, hydrogen bonded NO₃^– anions and π‐π stacking (phen)₂ dimers. The rare earth metal atoms are coordinated by four N atoms of two phen ligands and four O atoms of two H₂O molecules and two μ‐OH groups to complete tetragonal antiprisms. Via two common μ‐OH groups, two neighboring tetragonal antiprisms are condensed to a centrosymmetric dinuclear [Ln₂(phen)₄(H₂O)₄(OH)₂]⁴⁺ complex cation. Based on π‐π stacking interactions and hydrogen bonding, the complex cations and (phen)₂ dimers form 2 D layers parallel to (1 0 1), between which the hydrogen bonded NO₃^– anions are sandwiched. The structures can be simplified into a distorted CsCl structure when {[Ln₂(phen)₄(H₂O)₄(OH)₂](NO₃)₄} and (phen)₂ are viewed as building units.     

Synthesis,crystal structure and characterization of a series of complexes constructed from coordinated Lanthanides(III) and the heteropolyanion [SiMo12O40]4−

The reaction of α-[SiMo₁₂O₄₀]^4? with trivalent cations Ln³⁺ and N-methyl-2-pyrrolidone leads to a series of complexes of formula [Ln(NMP)₄(H₂O) _n ]H[SiMo₁₂O₄₀]?·?2NMP?·?mH₂O [where Ln?=?La (1), Pr (2), Nd (3), Sm (4), Gd (5), n?=?4, Ln?=?Dy (6), Er (7), n?=?3. NMP?=?N-methyl-2-pyrrolidone]. The syntheses, X-ray crystal structures, IR, and ESR spectra and thermal properties of the complexes 1, 2, 4, 6, 7 have been reported previously. Here, we report X-ray crystal structures, IR, UV, ESR spectra and thermal properties of the complexes [Nd(NMP)₄(H₂O)₄]H[SiMo₁₂O₄₀]?·?2NMP?·?1.5H₂O (3), and [Gd(NMP)₄(H₂O)₄]H[SiMo₁₂O₄₀]?·?2NMP?·?H₂O (5). In addition, the electrochemical behaviour of this series of complexes in aqueous solution and aqueous-organic solution has been investigated and systematic comparisons have been made. All these complexes exhibit successive reduction process of the Mo atoms.     

Synthesis,crystal structures,and infrared spectroscopy of a series of lanthanide phosphonoacetate coordination polymers

Hydrothermal reactions of lanthanide chloride, phosphonoacetic acid (H₂O₃PCH₂COOH), and water in the presence of HCl provide a series of lanthanide coordination polymers. FT-IR spectra confirm that there are three kinds of structures among seven complexes, {[Ln₂(O₃PCH₂CO₂)₂(H₂O)₃]?·?H₂O}_∞ (type I) (Ln?=?La^III for 1; Pr^III for 2; Nd^III for 3 and Eu^III for 4), [Ln(O₃PCH₂CO₂)(H₂O)₂]_∞ (type II) (Ln?=?Tb^III for 5), and [Ln(O₃PCH₂CO₂)(H₂O)₂]_∞ (type III) (Ln?=?Ho^III for 6 and Yb^III for 7). Complexes 1–5 show 2-D 4,4,5,5-connected (4⁴?·?6²)(4⁵?·?6)(4⁶?·?6⁴)(4⁸?·?6²) topology networks and 2-D 4-connected (4⁴?·?6²) topology networks and then are further linked into 3-D supramolecular networks by hydrogen-bonding interactions; 6 and 7 both exhibit a 3-D 4-connected (4²?·?6³?·?8) topology with 1-D dumbbell-shaped channels. The results indicate infrared spectroscopy is in accord with the result of single-crystal X-ray analysis.     

Synthesis,structures and magnetic properties of cyano- and amide-bridged FeIII-LnIII tetranuclear heterometallic clusters

Three Fe^III₂Ln^III₂ tetranuclear heterometallic clusters, [H₄LGd(H₂O)Tp*Fe(CN)₃]₂·8H₂O·2MeOH (1) and [H₄LLn(MeOH)Tp*Fe(CN)₃]₂·6MeOH·2MeCN (Ln?=?Tb and Dy for 2 and 3, respectively, H₆L = N,N′-(2,6-pyridine-dicarboxyl)-disalicylhydrazide, Tp* = hydridotris(3,5dimethylpyrazol-1-yl)-borate), were synthesized by use of the [(Tp*)Fe(CN)₃]^? unit as a metalloligand toward LnCl₃ and H₆L species. Structural analyses reveal that Fe^III and Ln^III ions in all complexes are connected to each other by one cyanide to form a heterobinuclear unit of [Ln(H₄L)][(Tp*)Fe(CN)₃], which is dimerized through Ln–N–C?=?O–Ln interaction. Magnetic susceptibility measurements show weak antiferromagnetic interactions between cyano-bridged Fe^III and Gd^III ions and amide-bridged Gd^III ions are operative. Complex 1 displays the magnetocaloric effect with ?ΔS_m^max = 12.70 J·kg^?1·K^?1 at 4.0 K for ΔH?=?7 T. No single-molecule magnetic properties are observed for 2 or 3 down to 1.8 K.     

Pure trinuclear 4f single-molecule magnets: synthesis, structures, magnetism and ab initio investigation

A family of linear Dy₃ and Tb₃ clusters have been facilely synthesized from the reactions of DyCl₃, the polydentate 3‐methyloxysalicylaldoxime (MeOsaloxH₂) ligand with auxiliary monoanionic ligands, such as trichloroacetate, NO₃^?, OH^?, and Cl^?. Complexes 1 – 5 contain a nearly linear Ln₃ core, with similar Ln???Ln distances (3.6901(4)–3.7304(3) Å for the Dy₃ species, and 3.7273(3)–3.7485(5) Å for the Tb₃ species) and Ln???Ln???Ln angles of 157.036(8)–159.026(15)° for the Dy₃ species and 157.156(8)–160.926(15)° for the Tb₃ species. All three Ln centers are bridged by the two doubly‐deprotonated [MeOsalox]^2? ligands and two of the four [MeOsaloxH]^? ligands through the N,O‐η²‐oximato groups and the phenoxo oxygen atoms (Dy‐O‐Dy angles=102.28(16)–106.85(13)°; Tb‐O‐Tb angles=102.00(11)–106.62(11)°). The remaining two [MeOsaloxH]^? ligands each chelate an outer Ln^III center through their phenoxo oxygen and oxime nitrogen atoms. Magnetic studies reveal that both Dy₃ and Tb₃ clusters exhibit significant ferromagnetic interactions and that the Dy₃ species behave as single‐molecule magnets, expanding upon the recent reports of the pure 4f type SMMs.     

Synthesis,Structures, and Magnetic Properties of Zigzag Tetranuclear Lanthanide Complexes

Five isostructural tetranuclear lanthanide complexes with the general formula [Ln₄(teaH₂)₂(teaH)₂(NO₃)₆] · 2CH₃OH [Ln³⁺ = Dy³⁺ ( 1 ), Tb³⁺ ( 2 ), Ho³⁺ ( 3 ), Er³⁺ ( 4 ), and Gd³⁺ ( 5 )] were successfully synthesized by the reaction of various lanthanide nitrate and triethanolamine (teaH₃) ligand. Single crystal X-ray analyses reveal the eight-coordinate Ln³⁺ centers adopt a slightly distorted triangular dodecahedron geometry and nine-coordinate Ln³⁺ ions own an approximately capped square antiprism environment in similar zigzag Ln4 core. Magnetic studies demonstrate the presence of anitferromagnetic interactions between Ln³⁺ centers without obvious SMM behavior.     

Synthesis,crystal structures and NIR luminescence of sandwich-like tetradentate salophen phenoxo-bridged heterotrinuclear metal complexes

Six phenoxo-bridged tetradentate salophen heterotrinuclear Zn₂Ln complexes, [Ln(ZnL)₂(NO₃)₃(CH₃OH)₂]·CH₃OH·CH₂Cl₂ [Ln?=?Pr (1), Nd (2)] and [Ln(ZnL)₂(NO₃)₃(CH₃OH)]·CH₃OH·CH₂Cl₂ [Ln?=?Eu (3), Ho (4), Er (5), and Yb (6)], have been isolated from reactions of N,N′-bis(salicylidene)-1,2-(phenylene-diamine) with Ln(NO₃)₃6H₂O and Zn(OAc)₂2H₂O. X-ray diffraction analysis reveals that 1–6 are isomorphic with phenoxo-bridged, sandwich-like {Zn₂Ln} core. Near infrared (NIR) luminescence spectra show that 6 exhibits typical emission of Yb³⁺ upon excitation at the ligand-centered absorption band at 357?nm.     

A series of 3d–4f heterometallic MOFs: syntheses,structures, optical,and electrochemical properties

Abstract

A series of heterometallic metal-organic frameworks (MOFs) employing pyridine-2,6-dicarboxylate and 1,10-phenanthroline as ligands have been synthesized hydrothermally. In isostructural compounds 1–3 [Ln(pydc)₃Cu₂(phen)₄]·I·× H₂O (Ln?=?La (1), Nd (2), Dy (3); x?=?6, 5, 5), the metalloligand [Ln(pydc)₃] assembles with [Cu(phen)₂] units to construct a dodecanuclear cluster via Cu–O bonds and π–π interactions. The clusters are further stacked into three-dimensional supramolecular frameworks with nano-sized cavities. In [La(Hpydc)(pydc)₂Zn(phen)₃]·3H₂O (4), the metalloligand [Ln(Hpydc)(pydc)₂] assembles with [Zn(phen)₃] units to construct a tetranuclear cluster via electrostatic interaction and π–π interaction. This work reveals that the changes of lanthanide metalloligands and the coordination pattern of 3d transition centers would result in significant variation in the final structures. The thermal, optical, and electrochemical properties have been well investigated.     

Hydrothermal syntheses,structural characterization,and photoluminescent properties of five lanthanide coordination polymers

Five mixed-ligand coordination polymers, [Ln₂(PTCP)₂(m-BDC)₃] _n ?·?nH₂O (Ln?=?Pr (1), Sm (2), Eu (3), Tb (4), Dy (5); m-BDC?=?1,3-benzenedicarboxylate; PTCP?=?2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene), were synthesized and characterized by IR spectra, elemental analyses, thermogravimetric analyses, single-crystal X-ray diffraction, and solid-state photoluminescent spectra. X-ray crystallographic analyses reveal that the five complexes are 1-D structures based on dinuclear [Ln₂O₁₂N₄] units and further assembled into 3-D supramolecular networks by hydrogen bonds and π···π stacking interactions. The solids possess high thermal stabilities, with 3 and 4 exhibiting strong pure red and green characteristic emissions of Eu(III) and Tb(III) at room temperature.     

Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties

The use of the [Fe^III(AA)(CN)₄]^? complex anion as metalloligand towards the preformed [Cu^II(valpn)Ln^III]³⁺ or [Ni^II(valpn)Ln^III]³⁺ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H₂valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu^II(valpn)Ln^III(H₂O)₃(μ‐NC)₂Fe^III(phen)(CN)₂ {(μ‐NC)Fe^III(phen)(CN)₃}]NO₃ ? 7 H₂O}_n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃] ? NO₃ ? H₂O ? CH₃CN ( 4 ) were obtained with the [Cu^II(valpn)Ln^III]³⁺ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni^II(valpn)Ln^III(ONO₂)₂(H₂O)(μ‐NC)₃Fe^III(bipy)(CN)] ? 2 H₂O ? 2 CH₃CN}_n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [Ni^II(valpn)Ln^III]³⁺ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃]⁺, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {Fe^III(bipy)(CN)₄} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {Ni^II(valpn)Ln^III} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu^II?Ln^III ( 1 – 3 ) and Ni^II?Ln^III ( 5 – 7 ) units, as well as through the single cyanide bridge between the Fe^III and either Ni^II ( 5 – 7 ) or Cu^II ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τ_o) and energy barrier (E_a) through the Arrhenius equation being 2.0×10^?12 s and 29.1 cm^?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (Ni^II–Dy^III) and single cyanide (Fe^III–Ni^II) pathways are masked by the depopulation of the Stark levels of the Dy^III ion, this feature most likely accounting for the continuous decrease of χ_M T upon cooling observed for this last compound.