Особливості реалізації графічного конвеєру при візуалізації тривимірних моделей приміщень університету

В більшості систем комп‘ютерної графіки застосовується графічний конвеєр – логічна група послідовно виконуваних обчислень (етапів), які в результаті дають синтезовану сцену на екрані комп‘ютера. Серед основних – етапи геометричних перетворень та візуалізації. Результат виконання кожного з цих етапів впливає на кінцевий вигляд синтезованої сцени, тому їх коректне завершення є необхідною умовою отримання якісного зображення

Solid-State Coordinative Behavior of a New Asymmetrical Bis-hydrazone Ligand Containing Two Different Binding Pockets

The potentially multidentate (O₂N–NO) trianionic bis­(bencylhydrazone) derived from 4-hydroxyisophthaldehyde (<b>H</b>_<b>3</b><b>L</b>) ligand has been synthesized and characterized. The coordinative behavior of the ligand has been explored toward different M^II salts (M = Co, Ni, Zn, and Cu), and four complexes, of general formula [M­(HL)]·solv (<b>2</b>·solv = molecules of water, dmf, or dmso), have been isolated and characterized. Furthermore, the species [M­(H₂L)₂]·solv (M = Co, <b>1a</b>·solv; M = Ni, <b>1b</b>·solv; solv = molecules of water and/or dmf), where the ligand is monodeprotonated and tridentate, has also been detected. The structures of <b>H</b>_<b>3</b><b>L</b>, four solvates of {[Cu­(HL)]·solv}_<i>n</i> (<b>2c</b>·solv), <b>1a</b>·5H₂O, and <b>1b</b>·H₂O·3dmf were determined by single-crystal X-ray diffraction. The effect of weak interactions on the crystal packing has also been analyzed. The thermal stability and the structural dynamics of the <b>2c</b>·solv systems have also been investigated

Two-Dimensional 3d–4f Heterometallic Coordination Polymers: Syntheses, Crystal Structures, and Magnetic Properties of Six New Co(II)–Ln(III) Compounds

Six new heterometallic cobalt­(II)-lanthanide­(III) complexes of formulas [Ln­(bta)­(H₂O)₂]₂[Co­(H₂O)₆]·10H₂O [Ln = Nd­(III) (<b>1</b>) and Eu­(III) (<b>2</b>)] and [Ln₂Co­(bta)₂(H₂O)₈]_<i>n</i>·6<i>n</i>H₂O [Ln = Eu­(III) (<b>3</b>), Sm­(III) (<b>4</b>), Gd­(III) (<b>5</b>), and Tb­(III) (<b>6</b>)] (H₄bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. <b>1</b> and <b>2</b> are isostructural compounds with a structure composed of anionic layers of [Ln­(bta)­(H₂O)₂]_<i>n</i>^<i>n</i>– sandwiching mononuclear [Co­(H₂O)₆]²⁺ cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. <b>3</b>–<b>6</b> are also isostructural compounds, and their structure consists of neutral layers of formula [Ln₂Co­(bta)₂(H₂O)₈]_<i>n</i> and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide­(III) polyhedra [Ln­(III)­O₉] and one compressed cobalt­(II) octahedron [Co­(II)­O₆] along the crystallographic <i>c</i>-axis are cross-linked by bta ligands within each layer of <b>3</b>–<b>6</b>. Magnetic susceptibility measurements on polycrystalline samples for <b>3</b>–<b>6</b> have been carried out in the temperature range of 2.0–300 K. The magnetic behavior of these types of Ln­(III)–Co­(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for <b>3</b> and <b>4</b>, and the occurrence of weak antiferromagnetic interactions within the Gd­(III)−Gd­(III) (<b>5</b>) and Tb­(III)−Tb­(III) (<b>6</b>) dinuclear units through the exchange pathway provided by the double oxo­(carboxylate) and double syn–syn carboxylate bridges

Two-Dimensional 3d–4f Heterometallic Coordination Polymers: Syntheses, Crystal Structures, and Magnetic Properties of Six New Co(II)–Ln(III) Compounds

Six new heterometallic cobalt­(II)-lanthanide­(III) complexes of formulas [Ln­(bta)­(H₂O)₂]₂[Co­(H₂O)₆]·10H₂O [Ln = Nd­(III) (<b>1</b>) and Eu­(III) (<b>2</b>)] and [Ln₂Co­(bta)₂(H₂O)₈]_<i>n</i>·6<i>n</i>H₂O [Ln = Eu­(III) (<b>3</b>), Sm­(III) (<b>4</b>), Gd­(III) (<b>5</b>), and Tb­(III) (<b>6</b>)] (H₄bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. <b>1</b> and <b>2</b> are isostructural compounds with a structure composed of anionic layers of [Ln­(bta)­(H₂O)₂]_<i>n</i>^<i>n</i>– sandwiching mononuclear [Co­(H₂O)₆]²⁺ cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. <b>3</b>–<b>6</b> are also isostructural compounds, and their structure consists of neutral layers of formula [Ln₂Co­(bta)₂(H₂O)₈]_<i>n</i> and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide­(III) polyhedra [Ln­(III)­O₉] and one compressed cobalt­(II) octahedron [Co­(II)­O₆] along the crystallographic <i>c</i>-axis are cross-linked by bta ligands within each layer of <b>3</b>–<b>6</b>. Magnetic susceptibility measurements on polycrystalline samples for <b>3</b>–<b>6</b> have been carried out in the temperature range of 2.0–300 K. The magnetic behavior of these types of Ln­(III)–Co­(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for <b>3</b> and <b>4</b>, and the occurrence of weak antiferromagnetic interactions within the Gd­(III)−Gd­(III) (<b>5</b>) and Tb­(III)−Tb­(III) (<b>6</b>) dinuclear units through the exchange pathway provided by the double oxo­(carboxylate) and double syn–syn carboxylate bridges

Synthesis, Crystal Structure and Magnetic Characterization of a Series of Cu^II–Ln^III Heterometallic [Ln = La, Ce, Pr, Nd and Sm) Metal–Organic Compounds with an Unusual Single Crystal to Single Crystal Phase Transition

The synthesis and structural characterization of five Cu­(II)–Ln­(III) heteronuclear metal–organic frameworks of formula {[Ln₄Cu₄(H₂O)₂₆(bta)₅]·<i>m</i>H₂O}_<i>n</i> and {[Ln₄Cu₄(H₂O)₂₄(bta)₅]·<i>p</i>H₂O}_<i>n</i> [Ln = La^III (<b>1A</b>/<b>1B</b>), Ce^III (<b>2A</b>/<b>2B</b>), Pr^III (<b>3A</b>/<b>3B</b>), Nd^III (<b>4A</b>/<b>4B</b>) and Sm^III (<b>5A</b>/<b>5B</b>) with m/p = 20 (<b>1A</b>)/16 (<b>1B</b>), 18 (<b>2A</b>)/16 (<b>2B</b>), 14 (<b>3A</b>)/16 (<b>3B</b>), 22 (<b>4A</b>)/16 (<b>4B</b>) and 21 (<b>5A</b>)/14 (<b>5B</b>); H₄bta =1,2,4,5-benzenetetracarboxylic acid (<b>1</b>–<b>5</b>)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded <b>A</b> phases toward the <b>B</b> shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the crystallographic <i>b</i>-axis in the range 2.4 to 2.8 Å with the consequent decrease of the unit cell volume from 9.5% to 12%. The isomorphous crystal structures of <b>1A</b>–<b>5A</b> can be described as two crystallographically independent [Cu­(II)–Ln­(III)] heterometallic dinuclear units which are connected through two crystallographically independent bta^4– ligands in the <i>ac</i>-plane, leading to 4,4-rectangular grids. These layers are connected along the crystallographic <i>b</i>-axis, through a pillaring bta^4– group. The phase transition implies a change of the coordination mode of the bta^4– pillar from bis-monodentate (<b>1A</b>–<b>5A</b>) to tetrakis-monodentate (<b>1B</b>–<b>5B</b>). Magnetic susceptibility measurements of polycrystalline samples of <b>1A</b>–<b>5A</b> in the temperature range 2.0–300 K have in common the decrease of the χ_M<i>T</i> product with <i>T</i> which in the case of <b>1A</b> is due to weak antiferromagnetic interactions between the copper­(II) ions through the bta^4– skeleton, the La^III cation being diamagnetic [<i>J</i> = −3.5 cm^–1 with the Hamiltonian defined <i><b>H</b></i> = −<i>J<b>S</b></i>_Cu1·<i><b>S</b></i>_Cu2]. For the <b>2A</b>–<b>5A</b> compounds, the additional exchange interaction between Cu^II and the paramagnetic Ln^III is masked by the crystal field effects (which partially removes the 2<i>J</i> + 1 degeneracy of the ^2<i>S</i>+1<i>L</i>_<i>J</i> free-ion ground state in zero magnetic field) (<b>2A</b>–<b>5A</b>) and the thermal population of excited free-ion states (<b>5A</b>)

Synthesis, crystal structure and magnetic characterization of a series of CuII-LnIII heterometallic [Ln = La, Ce, Pr, Nd and Sm) metal-organic compounds with an unusual single crystal to single crystal phase transition

The synthesis and structural characterization of five Cu(II)-Ln(III) heteronuclear metal-organic frameworks of formula {[Ln4Cu 4(H2O)26(bta)5]·mH 2O}n and {[Ln4Cu4(H 2O)24(bta)5]·pH2O} n [Ln = LaIII (1A/1B), CeIII (2A/2B), Pr III (3A/3B), NdIII (4A/4B) and SmIII (5A/5B) with m/p = 20 (1A)/16 (1B), 18 (2A)/16 (2B), 14 (3A)/16 (3B), 22 (4A)/16 (4B) and 21 (5A)/14 (5B); H4bta =1,2,4,5-benzenetetracarboxylic acid (1-5)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded A phases toward the B shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the crystallographic b-axis in the range 2.4 to 2.8 Å with the consequent decrease of the unit cell volume from 9.5% to 12%. The isomorphous crystal structures of 1A-5A can be described as two crystallographically independent [Cu(II)-Ln(III)] heterometallic dinuclear units which are connected through two crystallographically independent bta4- ligands in the ac-plane, leading to 4,4-rectangular grids. These layers are connected along the crystallographic b-axis, through a pillaring bta4- group. The phase transition implies a change of the coordination mode of the bta4- pillar from bis-monodentate (1A-5A) to tetrakis-monodentate (1B-5B). Magnetic susceptibility measurements of polycrystalline samples of 1A-5A in the temperature range 2.0-300 K have in common the decrease of the χMT product with T which in the case of 1A is due to weak antiferromagnetic interactions between the copper(II) ions through the bta 4- skeleton, the LaIII cation being diamagnetic [J = -3.5 cm-1 with the Hamiltonian defined H = -JSCu1·S Cu2]. For the 2A-5A compounds, the additional exchange interaction between CuII and the paramagnetic LnIII is masked by the crystal field effects (which partially removes the 2J + 1 degeneracy of the 2S+1LJ free-ion ground state in zero magnetic field) (2A-5A) and the thermal population of excited free-ion states (5A). © 2013 American Chemical Society.Funding for this work was partially provided Ministerio Español de Economia y Competitividad through Projects MAT2010-16981, MAT2011-27233-C0-02, DPI2010-21103-C04-03, CTQ2010-15364 and “Factoría de Cristalización” (Consolider- Ingenio2010, CSD2006-00015), the Gobierno de Canarias through projects PIL2070901 and structuring NANOMAC and the Generalitat Valenciana (PROMETEO2009/108 and ISIC/2012/002). P.D-G. and J.P. also thank Ministerio Español de Economia y Competitividad through FPI program and the NANOMAC project for predoctoral and postdoctoral contracts, respectively.Peer Reviewe

Novel Malonate-Containing Coordination Compounds with Ligands Having N- and NO-Donors: Synthesis, Structures, and Magnetic Properties

In our efforts to tune the structures of mixed-ligands malonate-containing coordination compounds, four copper(II) and two high-spin cobalt(II) complexes of formulas [Cu(mal)(H₂O)(dpo)]_<i>n</i> <b>(1)</b>, [Cu₂(mal)₂(H₂O)₂(dpp)]_<i>n</i>·7<i>n</i>H₂O <b>(2)</b>, [Cu₂(mal)₂(H₂O)₂(bpe)]_<i>n</i>·2<i>n</i>H₂O <b>(3)</b>, {[Cu(mal)₂(H₂O)₂][Cu(dien)]}_<i>n</i>·4<i>n</i>H₂O <b>(4)</b> [Co₂(mal)₂(H₂O)₆(dpo)]·2H₂O <b>(5)</b> and [Co(mal)(H₂O)(phen)]_<i>n</i>·2<i>n</i>H₂O <b>(6)</b> [H₂mal = malonic acid, dpo =4,4′-bipyridine-<i>N</i>,<i>N′</i>-dioxide, dpp = 2,3-bis(pyridyl)pyrazine, bpe =1,2-bis(4-pyridyl)ethylene, dien = diethylenetriamine and phen = 1,10-phenanthroline] have been synthesized and structurally characterized by X-ray diffraction on single crystals. Complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b> are chain compounds, <b>5</b> is a dinuclear species, and <b>3</b> has a sheet-like structure. The malonate ligand in this family acts as either a blocking (<b>1</b> and <b>5</b>) or bridging ligand (<b>2</b>–<b>6</b>). The rod-like molecules dpo (<b>1</b> and <b>5</b>) and bpe (<b>3</b>) exhibit the bis-monodentate (<b>1</b> and <b>3</b>) and monodentate (<b>5</b>) coordination modes, whereas dpp (<b>2</b>), dien (<b>4</b>), and phen (<b>6</b>) act as bis-bidentate (<b>2</b>), tridentate (<b>4</b>), and bidentate (<b>6</b>) ligands. The neutral motifs of <b>1</b>–<b>6</b> are interlinked through hydrogen bonds and weak C–H···π and π–π type interactions affording supramolecular three-dimensional networks. Variable-temperature magnetic susceptibility measurements show the occurrence of weak ferro- (<b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b>) and antiferromagnetic (<b>1</b> and <b>4</b>) interactions, the exchange pathways being the carboxylate-malonate (<b>3</b>–<b>6</b>), oxo-carboxylate (<b>2</b>), bis-bidentate (dpp) (<b>2</b>) or hydrogen bonds (<b>1</b>). Remarkably, the equatorial-apical exchange pathway through the carboxylate bridge present in <b>4</b> provides the first case of the occurrence of an antiferromagnetic interaction in a malonate-containing copper(II) complex

Novel Malonate-Containing Coordination Compounds with Ligands Having N- and NO-Donors: Synthesis, Structures, and Magnetic Properties

In our efforts to tune the structures of mixed-ligands malonate-containing coordination compounds, four copper(II) and two high-spin cobalt(II) complexes of formulas [Cu(mal)(H₂O)(dpo)]_<i>n</i> <b>(1)</b>, [Cu₂(mal)₂(H₂O)₂(dpp)]_<i>n</i>·7<i>n</i>H₂O <b>(2)</b>, [Cu₂(mal)₂(H₂O)₂(bpe)]_<i>n</i>·2<i>n</i>H₂O <b>(3)</b>, {[Cu(mal)₂(H₂O)₂][Cu(dien)]}_<i>n</i>·4<i>n</i>H₂O <b>(4)</b> [Co₂(mal)₂(H₂O)₆(dpo)]·2H₂O <b>(5)</b> and [Co(mal)(H₂O)(phen)]_<i>n</i>·2<i>n</i>H₂O <b>(6)</b> [H₂mal = malonic acid, dpo =4,4′-bipyridine-<i>N</i>,<i>N′</i>-dioxide, dpp = 2,3-bis(pyridyl)pyrazine, bpe =1,2-bis(4-pyridyl)ethylene, dien = diethylenetriamine and phen = 1,10-phenanthroline] have been synthesized and structurally characterized by X-ray diffraction on single crystals. Complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b> are chain compounds, <b>5</b> is a dinuclear species, and <b>3</b> has a sheet-like structure. The malonate ligand in this family acts as either a blocking (<b>1</b> and <b>5</b>) or bridging ligand (<b>2</b>–<b>6</b>). The rod-like molecules dpo (<b>1</b> and <b>5</b>) and bpe (<b>3</b>) exhibit the bis-monodentate (<b>1</b> and <b>3</b>) and monodentate (<b>5</b>) coordination modes, whereas dpp (<b>2</b>), dien (<b>4</b>), and phen (<b>6</b>) act as bis-bidentate (<b>2</b>), tridentate (<b>4</b>), and bidentate (<b>6</b>) ligands. The neutral motifs of <b>1</b>–<b>6</b> are interlinked through hydrogen bonds and weak C–H···π and π–π type interactions affording supramolecular three-dimensional networks. Variable-temperature magnetic susceptibility measurements show the occurrence of weak ferro- (<b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b>) and antiferromagnetic (<b>1</b> and <b>4</b>) interactions, the exchange pathways being the carboxylate-malonate (<b>3</b>–<b>6</b>), oxo-carboxylate (<b>2</b>), bis-bidentate (dpp) (<b>2</b>) or hydrogen bonds (<b>1</b>). Remarkably, the equatorial-apical exchange pathway through the carboxylate bridge present in <b>4</b> provides the first case of the occurrence of an antiferromagnetic interaction in a malonate-containing copper(II) complex

Novel Malonate-Containing Coordination Compounds with Ligands Having N- and NO-Donors: Synthesis, Structures, and Magnetic Properties

In our efforts to tune the structures of mixed-ligands malonate-containing coordination compounds, four copper(II) and two high-spin cobalt(II) complexes of formulas [Cu(mal)(H₂O)(dpo)]_<i>n</i> <b>(1)</b>, [Cu₂(mal)₂(H₂O)₂(dpp)]_<i>n</i>·7<i>n</i>H₂O <b>(2)</b>, [Cu₂(mal)₂(H₂O)₂(bpe)]_<i>n</i>·2<i>n</i>H₂O <b>(3)</b>, {[Cu(mal)₂(H₂O)₂][Cu(dien)]}_<i>n</i>·4<i>n</i>H₂O <b>(4)</b> [Co₂(mal)₂(H₂O)₆(dpo)]·2H₂O <b>(5)</b> and [Co(mal)(H₂O)(phen)]_<i>n</i>·2<i>n</i>H₂O <b>(6)</b> [H₂mal = malonic acid, dpo =4,4′-bipyridine-<i>N</i>,<i>N′</i>-dioxide, dpp = 2,3-bis(pyridyl)pyrazine, bpe =1,2-bis(4-pyridyl)ethylene, dien = diethylenetriamine and phen = 1,10-phenanthroline] have been synthesized and structurally characterized by X-ray diffraction on single crystals. Complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b> are chain compounds, <b>5</b> is a dinuclear species, and <b>3</b> has a sheet-like structure. The malonate ligand in this family acts as either a blocking (<b>1</b> and <b>5</b>) or bridging ligand (<b>2</b>–<b>6</b>). The rod-like molecules dpo (<b>1</b> and <b>5</b>) and bpe (<b>3</b>) exhibit the bis-monodentate (<b>1</b> and <b>3</b>) and monodentate (<b>5</b>) coordination modes, whereas dpp (<b>2</b>), dien (<b>4</b>), and phen (<b>6</b>) act as bis-bidentate (<b>2</b>), tridentate (<b>4</b>), and bidentate (<b>6</b>) ligands. The neutral motifs of <b>1</b>–<b>6</b> are interlinked through hydrogen bonds and weak C–H···π and π–π type interactions affording supramolecular three-dimensional networks. Variable-temperature magnetic susceptibility measurements show the occurrence of weak ferro- (<b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b>) and antiferromagnetic (<b>1</b> and <b>4</b>) interactions, the exchange pathways being the carboxylate-malonate (<b>3</b>–<b>6</b>), oxo-carboxylate (<b>2</b>), bis-bidentate (dpp) (<b>2</b>) or hydrogen bonds (<b>1</b>). Remarkably, the equatorial-apical exchange pathway through the carboxylate bridge present in <b>4</b> provides the first case of the occurrence of an antiferromagnetic interaction in a malonate-containing copper(II) complex

Novel Malonate-Containing Coordination Compounds with Ligands Having N- and NO-Donors: Synthesis, Structures, and Magnetic Properties

In our efforts to tune the structures of mixed-ligands malonate-containing coordination compounds, four copper(II) and two high-spin cobalt(II) complexes of formulas [Cu(mal)(H₂O)(dpo)]_<i>n</i> <b>(1)</b>, [Cu₂(mal)₂(H₂O)₂(dpp)]_<i>n</i>·7<i>n</i>H₂O <b>(2)</b>, [Cu₂(mal)₂(H₂O)₂(bpe)]_<i>n</i>·2<i>n</i>H₂O <b>(3)</b>, {[Cu(mal)₂(H₂O)₂][Cu(dien)]}_<i>n</i>·4<i>n</i>H₂O <b>(4)</b> [Co₂(mal)₂(H₂O)₆(dpo)]·2H₂O <b>(5)</b> and [Co(mal)(H₂O)(phen)]_<i>n</i>·2<i>n</i>H₂O <b>(6)</b> [H₂mal = malonic acid, dpo =4,4′-bipyridine-<i>N</i>,<i>N′</i>-dioxide, dpp = 2,3-bis(pyridyl)pyrazine, bpe =1,2-bis(4-pyridyl)ethylene, dien = diethylenetriamine and phen = 1,10-phenanthroline] have been synthesized and structurally characterized by X-ray diffraction on single crystals. Complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b> are chain compounds, <b>5</b> is a dinuclear species, and <b>3</b> has a sheet-like structure. The malonate ligand in this family acts as either a blocking (<b>1</b> and <b>5</b>) or bridging ligand (<b>2</b>–<b>6</b>). The rod-like molecules dpo (<b>1</b> and <b>5</b>) and bpe (<b>3</b>) exhibit the bis-monodentate (<b>1</b> and <b>3</b>) and monodentate (<b>5</b>) coordination modes, whereas dpp (<b>2</b>), dien (<b>4</b>), and phen (<b>6</b>) act as bis-bidentate (<b>2</b>), tridentate (<b>4</b>), and bidentate (<b>6</b>) ligands. The neutral motifs of <b>1</b>–<b>6</b> are interlinked through hydrogen bonds and weak C–H···π and π–π type interactions affording supramolecular three-dimensional networks. Variable-temperature magnetic susceptibility measurements show the occurrence of weak ferro- (<b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b>) and antiferromagnetic (<b>1</b> and <b>4</b>) interactions, the exchange pathways being the carboxylate-malonate (<b>3</b>–<b>6</b>), oxo-carboxylate (<b>2</b>), bis-bidentate (dpp) (<b>2</b>) or hydrogen bonds (<b>1</b>). Remarkably, the equatorial-apical exchange pathway through the carboxylate bridge present in <b>4</b> provides the first case of the occurrence of an antiferromagnetic interaction in a malonate-containing copper(II) complex