2D-Coordination Polymer Containing Interconnected 82-Membered Organotin Macrocycles

A two-dimensional coordination polymer [(<i>n</i>-Bu₃Sn)₄(μ-L)₂(4,4′-bipy)]_<i>n</i> (<b>1</b>) was prepared in a reaction between (<i>n</i>-Bu₃Sn)₂O, (<i>E</i>)-5-(pyridin-4-yl-methyleneamino)­isophthalic acid (LH₂), and 4,4′-bipyridine (4,4′-bipy). The structure of <b>1</b> is built by the interlinking of 82-membered macrocyles. The generation of the 2D coordination polymer is facilitated by the multisite coordination capability of the dianionic ligand (L^2–) as well as involvement of 4,4′-bipyridine as an ancillary ligand

2D-Coordination Polymer Containing Interconnected 82-Membered Organotin Macrocycles

A two-dimensional coordination polymer [(<i>n</i>-Bu₃Sn)₄(μ-L)₂(4,4′-bipy)]_<i>n</i> (<b>1</b>) was prepared in a reaction between (<i>n</i>-Bu₃Sn)₂O, (<i>E</i>)-5-(pyridin-4-yl-methyleneamino)­isophthalic acid (LH₂), and 4,4′-bipyridine (4,4′-bipy). The structure of <b>1</b> is built by the interlinking of 82-membered macrocyles. The generation of the 2D coordination polymer is facilitated by the multisite coordination capability of the dianionic ligand (L^2–) as well as involvement of 4,4′-bipyridine as an ancillary ligand

Two-Dimensional Homometallic- to a Three Dimensional Heterometallic Coordination Polymer: A Metalloligand Approach

A metalloligand type of synthetic route has been followed to generate a novel heterometallic three-dimensional (3D)-coordination polymer containing Cu­(II) and trimethyltin as nodes. The first step of this synthetic path consisted of the preparation of a two-dimensional-coordination polymer of Cu­(II), [Cu­(μ-LH)₂]_<i>n</i> (<b>1</b>) (LH₂ = pyridine-2,5-dicarboxylic acid). The reaction of in situ generated <b>1</b> with Me₃SnCl afforded the heterometallic 3D-coordination polymer, [Cu­(Me₃Sn)₂(μ-L)₂]_<i>n</i> (<b>2</b>). The latter is a 4,4-connected polymer with a <i>sqc</i> topology. This 3D-framework contains a paddle-wheel-shaped core comprised of two heterometallic (Cu^II/Sn^IV) macrocycles

η⁶‑Benzene(tricarbonyl)chromium and Cymantrene Assemblies Supported on an Organostannoxane Platform

A series of η⁶-benzene­(tricarbonyl)chromium and cymantrene-containing [cymantrene = cyclopentadienylmanganese­(I) tricarbonyl] assemblies supported on organostannoxane platforms are reported. The reaction of [Cr­(η⁶-C₆H₅CO₂H)(CO)₃] (L1H) with <i>n</i>-Bu₂SnCl₂ in a 1:1 ratio afforded the tetranuclear derivative [{<i>n</i>-Bu₂Sn}₂(μ₃-O)­(μ-OMe)­(L1)]₂ (<b>1</b>) whereas a similar reaction carried out in a 2:1 stoichiometry afforded the mononuclear derivative [<i>n</i>-Bu₂Sn­(L1)₂] (<b>2</b>). The reaction of (<i>t</i>-Bu₂SnO)₃ with L1H in toluene in a 1:3 ratio afforded the hydroxide-bridged dimer, [<i>t</i>-Bu₂Sn­(μ-OH)­(L1)]₂ (<b>3</b>). A 1:2 reaction between [{η⁶-C₆H₄(COOH)₂<b>-</b>1,3}­Cr­(CO)₃] (L2H₂) and Me₃SnCl afforded a two-dimensional coordination polymer [{Me₃Sn}₂(μ₄-L2)]_<i>n</i> (<b>4</b>). A similar reaction between [{η⁶-C₆H₄(COOH)₂<b>-</b>1,4}­Cr­(CO)₃] (L3H₂) and Me₃SnCl in a 1:2 ratio also afforded a two-dimensional coordination polymer [{Me₃Sn}₂(μ₄-L3)]_<i>n</i> (<b>5</b>). The reaction of L3H₂ with Me₃SnCl in the presence of 4,4′-bipyridine afforded a 1D-coordination polymer [(Me₃Sn)₂(μ-L3)­(μ-4,4′-bipy)]_<i>n</i> (<b>6</b>). The reaction of L3H₂ with (Ph₃Sn)₂O (in a 1:1 ratio) gave a dimer [(H₂O)­SnPh₃(μ-L3)­SnPh₃(MeOH)] (<b>7</b>). The 1:1 reaction of [Mn­(η⁵-C₅H₄COOH)(CO)₃] (L4H) with Me₂SnCl₂ yielded the tetranuclear derivative [{Me₂Sn}₂(μ₃-O)­(L4)₂]₂ (<b>8</b>). A similar reaction of [Mn­{η⁵-C₅H₄C­(O)­CH₂CH₂COOH}­(CO)₃] (L5H) with Me₂SnCl₂ in a 1:1 ratio also afforded a tetrameric derivative [{Me₂Sn}₂(μ₃-O)­(μ₂-OMe)­(L5)]₂ (<b>9</b>). All the compounds were characterized by single crystal X-ray diffraction. Complexes <b>4</b> and <b>5</b> are planar organometallic 2D-coordination polymers

Molecular Indium(III) Phosphonates Possessing Ring and Cage Structures. Synthesis and Structural Characterization of [In₂(<i>t</i>‑BuPO₃H)₄(phen)₂Cl₂] and [In₃(C₅H₉PO₃)₂(C₅H₉PO₃H)₄(phen)₃]·NO₃·3.5H₂O

Two novel indium­(III) phosphonates, [In₂(<i>t</i>-BuPO₃H)₄(phen)₂Cl₂] (<b>1</b>) and [In₃(C₅H₉PO₃)₂(C₅H₉PO₃H)₄(phen)₃]·NO₃·3.5H₂O (<b>2</b>) with phen = 1,10-phenanthroline, have been synthesized by solvothermal reactions involving indium­(III) salts and organophosphonic acids. <b>1</b> is a dinuclear compound where the two indium centers are bridged by a pair of isobidentate phosphonate ligands, [<i>t</i>-BuP­(O)₂OH]⁻, resulting in an eight-membered (In₂P₂O₄) puckered ring. Compound <b>2</b> is trinuclear; the In₃ platform is held together by two bicapping tripodal phosphonate ligands from the top and bottom of the indium plane. In addition, two bridging monoanionic phosphonate ligands serve to bind two pairs of indium centers. Both <b>1</b> and <b>2</b> also contain monodentate monoanionic phosphonate ligands. The solid-state MAS ³¹P NMR spectrum of complex <b>1</b> shows two signals at 21.9 and 29.3 ppm. Compound <b>2</b> contains signal maxima at 25.8 and 28.9 ppm, with a shoulder at 31.5 ppm. Room temperature solid-state fluorescence spectra of <b>1</b> and <b>2</b> are characterized by strong emission bands at 385 nm (λ_ex = 350 nm) and 395 nm (λ_ex = 350 nm), respectively, which are red-shifted with respect to the emission of free phenanthroline

Octanuclear {Ln(III)₈}(Ln = Gd, Tb, Dy, Ho) Macrocyclic Complexes in a Cyclooctadiene-like Conformation: Manifestation of Slow Relaxation of Magnetization in the Dy(III) Derivative

The synthesis of a series of macrocyclic, isostructural octanuclear lanthanide complexes [Gd₈ (LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·6CH₃OH·2H₂O (<b>1</b>), [Tb₈ (LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]₄CH₃OH·4H₂O (<b>2</b>), [Dy₈(LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·8CH₃OH (<b>3</b>), and [Ho₈(LH₂)₄(μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·CH₃OH·4H₂O (<b>4</b>) have been achieved, using Ln­(III) nitrate salts, pivalic acid, and a new multidentate chelating ligand (2<i>E</i>,<i>N</i>′<i>E</i>)-<i>N</i>′-(3-((bis­(2- hydroxyethyl)­amino)­methyl)-2-hydroxy-5-methylbenzylidene)-2-(hydroxyimino) propane hydrazide (LH₅), containing two unsymmetrically disposed arms; one side of the phenol unit is decorated with a diethanolamine group while the other side is a hydrazone that has been built by the condensation reaction involving 2-hydroxyiminopropanehydrazide. All the compounds, <b>1</b>–<b>4</b>, are neutral and are held by the four [LH₂]^3– triply deprotonated chelating ligands. In these complexes all the lanthanide ions are doubly or triply bridged via phenolate, alkoxy, and pivalate oxygens. The metal centers are distributed over the 8 vertices of an octagon, resembling a cyclooctadiene ring core. The details of magnetochemical analysis for complexes <b>1</b>–<b>4</b> shows that they exhibit antiferromagnetic interactions between the Ln³⁺ ions through the phenoxo, alkoxo, and pivalato bridging groups. None of the compounds exhibits slow relaxation of the magnetization at zero applied direct current (dc) magnetic field, which could be due to the existence of a fast quantum tunneling relaxation of the magnetization (QTM). In the case of <b>3</b>, the application of a small dc field is enough as to fully or partly suppress the fast and efficient zero-field QTM allowing the observation of slow relaxation above 2 K

Molecular Indium(III) Phosphonates Possessing Ring and Cage Structures. Synthesis and Structural Characterization of [In₂(<i>t</i>‑BuPO₃H)₄(phen)₂Cl₂] and [In₃(C₅H₉PO₃)₂(C₅H₉PO₃H)₄(phen)₃]·NO₃·3.5H₂O

Two novel indium­(III) phosphonates, [In₂(<i>t</i>-BuPO₃H)₄(phen)₂Cl₂] (<b>1</b>) and [In₃(C₅H₉PO₃)₂(C₅H₉PO₃H)₄(phen)₃]·NO₃·3.5H₂O (<b>2</b>) with phen = 1,10-phenanthroline, have been synthesized by solvothermal reactions involving indium­(III) salts and organophosphonic acids. <b>1</b> is a dinuclear compound where the two indium centers are bridged by a pair of isobidentate phosphonate ligands, [<i>t</i>-BuP­(O)₂OH]⁻, resulting in an eight-membered (In₂P₂O₄) puckered ring. Compound <b>2</b> is trinuclear; the In₃ platform is held together by two bicapping tripodal phosphonate ligands from the top and bottom of the indium plane. In addition, two bridging monoanionic phosphonate ligands serve to bind two pairs of indium centers. Both <b>1</b> and <b>2</b> also contain monodentate monoanionic phosphonate ligands. The solid-state MAS ³¹P NMR spectrum of complex <b>1</b> shows two signals at 21.9 and 29.3 ppm. Compound <b>2</b> contains signal maxima at 25.8 and 28.9 ppm, with a shoulder at 31.5 ppm. Room temperature solid-state fluorescence spectra of <b>1</b> and <b>2</b> are characterized by strong emission bands at 385 nm (λ_ex = 350 nm) and 395 nm (λ_ex = 350 nm), respectively, which are red-shifted with respect to the emission of free phenanthroline

A 30-Membered Nonanuclear Cobalt(II) Macrocycle Containing Phosphonate-Bridged Trinuclear Subunits

The reaction of Co­(ClO₄)₂·6H₂O with (trichloromethyl)­phosphonic acid and 3,5-dimethyl-1<i>H</i>-pyrazole in a 3:1:6 ratio in the presence of triethylamine afforded [Co₉(3,5-DMPz)₁₂­(3,5-DMPzH)₆­(Cl₃CPO₃)₃]­(toluene)₇ (<b>1</b>). The latter contains three trinuclear (Co₃) subunits which are linked to each other by three bridging phosphonate ligands affording a 30-membered macrocycle. <b>1</b> contains an equilateral triangle comprising the phosphorus atoms of the bridging phosphonate groups. In solution, <b>1</b> breaks down into the trinuclear subunits as detected by electrospray ionization mass spectrometry

Octanuclear {Ln(III)₈}(Ln = Gd, Tb, Dy, Ho) Macrocyclic Complexes in a Cyclooctadiene-like Conformation: Manifestation of Slow Relaxation of Magnetization in the Dy(III) Derivative

The synthesis of a series of macrocyclic, isostructural octanuclear lanthanide complexes [Gd₈ (LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·6CH₃OH·2H₂O (<b>1</b>), [Tb₈ (LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]₄CH₃OH·4H₂O (<b>2</b>), [Dy₈(LH₂)₄ (μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·8CH₃OH (<b>3</b>), and [Ho₈(LH₂)₄(μ-Piv)₄ (η²-Piv)₄ (μ-OMe)₄]·CH₃OH·4H₂O (<b>4</b>) have been achieved, using Ln­(III) nitrate salts, pivalic acid, and a new multidentate chelating ligand (2<i>E</i>,<i>N</i>′<i>E</i>)-<i>N</i>′-(3-((bis­(2- hydroxyethyl)­amino)­methyl)-2-hydroxy-5-methylbenzylidene)-2-(hydroxyimino) propane hydrazide (LH₅), containing two unsymmetrically disposed arms; one side of the phenol unit is decorated with a diethanolamine group while the other side is a hydrazone that has been built by the condensation reaction involving 2-hydroxyiminopropanehydrazide. All the compounds, <b>1</b>–<b>4</b>, are neutral and are held by the four [LH₂]^3– triply deprotonated chelating ligands. In these complexes all the lanthanide ions are doubly or triply bridged via phenolate, alkoxy, and pivalate oxygens. The metal centers are distributed over the 8 vertices of an octagon, resembling a cyclooctadiene ring core. The details of magnetochemical analysis for complexes <b>1</b>–<b>4</b> shows that they exhibit antiferromagnetic interactions between the Ln³⁺ ions through the phenoxo, alkoxo, and pivalato bridging groups. None of the compounds exhibits slow relaxation of the magnetization at zero applied direct current (dc) magnetic field, which could be due to the existence of a fast quantum tunneling relaxation of the magnetization (QTM). In the case of <b>3</b>, the application of a small dc field is enough as to fully or partly suppress the fast and efficient zero-field QTM allowing the observation of slow relaxation above 2 K

Stabilizing the [RSn(μ₂‑O)SnR] Motif through Intramolecular N→Sn Coordination. Synthesis and Characterization of [(RSn)₂(μ₂‑O)(μ₂‑FcCOO)₂(η-FcCOO)₂]·THF and {(RSn)₂(μ₂‑O)[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (R = 2‑(Phenylazo)phenyl)

The reactions of RSnCl₃ (<b>1</b>; R = 2-(phenylazo)­phenyl) with FcCOOH or di-<i>tert</i>-butyl phosphate in refluxing THF afforded the monoorganodistannoxanes [(RSn)₂(μ₂-O)­(μ₂-FcCOO)₂(η-FcCOO)₂]·THF (<b>2</b>) and {(RSn)₂(μ₂-O)­[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (<b>3</b>). The molecular structure of <b>2</b> contains seven-coordinate tin centers in a distorted-pentagonal-bipyramidal geometry, while <b>3</b> contains six-coordinate tin centers in a distorted-octahedral geometry. In the dinuclear compounds <b>2</b> and <b>3</b> the two tin centers are bridged by a μ₂-O unit, affording a rare Sn–O–Sn motif among monoorganostannoxanes. In addition, each tin is also intramolecularly coordinated to the nitrogen atom of the 2-phenylazophenyl substituent (N→Sn). Further, in <b>2</b>, the two tin centers are bridged by two isobidentate ferrocenecarboxylate ligands; each tin center also is bound to a chelating ferrocenecarboxylate ligand. On the other hand, in <b>3</b>, while the two tin centers are bridged by two isobidentate di-<i>tert</i>-butyl phosphate ligands, each tin center also has a terminal chloride ligand