Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates
Three series of mesogenic coordination polymers based on mixed-valent diruthenium tetracarboxylates, namely Ru 2 (3,4-B2OCn) 4 Cl, Ru 2 (3,5-B2OCn) 4 Cl and Ru 2 (3,4,5-B3OCn) 4 Cl [3,4-B2OCn = 3,4-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - , 3,5-B2OCn = 3,5-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - and 3,4,5-B3OCn = 3,...
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2009
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09599428_v19_n28_p4981_Chaia http://hdl.handle.net/20.500.12110/paper_09599428_v19_n28_p4981_Chaia |
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paper:paper_09599428_v19_n28_p4981_Chaia2023-06-08T15:57:13Z Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates Aliphatic chains Cl atoms Columnar mesophases Coordination Polymers Crystalline phase Crystallographic studies Dilatometry Diruthenium EXAFS Intermolecular space IR spectroscopy Lamellar mesophases Liquid-crystalline Liquid-crystalline phasis Local probes Magnetic susceptibility measurements Mesogenics Mesophases Mixed-valent Parallel arrangement Polarized optical microscopy Preorganization Resonance Raman Room temperature Structural arrangement Structural information Supramolecular architectures Thermal stability Variable temperature XRD Zig-zag Crystalline materials Differential scanning calorimetry Liquids Magnetic susceptibility Optical microscopy Ruthenium compounds X ray diffraction Polymers Three series of mesogenic coordination polymers based on mixed-valent diruthenium tetracarboxylates, namely Ru 2 (3,4-B2OCn) 4 Cl, Ru 2 (3,5-B2OCn) 4 Cl and Ru 2 (3,4,5-B3OCn) 4 Cl [3,4-B2OCn = 3,4-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - , 3,5-B2OCn = 3,5-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - and 3,4,5-B3OCn = 3,4,5-(C n H 2n+1 O) 3 C 6 H 2 CO 2 - ] have been synthesized and characterized, with the aim of obtaining columnar liquid crystalline phases. These equatorial BmOCn ligands have been selected under the assumption that they will efficiently fill the intermolecular space around the axial Cl atoms, thus warranting a parallel arrangement of the polymeric ⋯Ru 2 -Cl-Ru 2 -Cl⋯ strands in the crystalline phase, which should facilitate the occurrence of Col mesophases. The liquid crystalline character of the synthesized compounds has been studied by means of polarized optical microscopy, differential scanning calorimetry, and variable temperature X-ray diffraction. They all exhibit thermotropic Col H mesophases, the 3,4-B2OCn derivatives also exhibit a lamellar mesophase. Many of the studied compounds exhibit room temperature mesomorphism. The thermal stability domain of the Col H mesophases of the 3,5-B2OCn and 3,4,5-B3OCn derivatives is remarkably wide, from below 0 °C to ca. 300 °C in some cases. Based on pieces of structural information coming from XRD experiments, dilatometry, and local probes (magnetic susceptibility measurements, resonance Raman and IR spectroscopies, and Exafs) we suggest a model for the structural arrangement of the polymeric strands in the mesophase, in which the central polar backbone of the polymeric strands is in a zig-zag conformation, surrounded by a continuum of molten aliphatic chains. A crystallographic study of the non-mesogenic light homologue Ru 2 (3,4,5-B3OC2) 4 Cl confirms these aspects of the model, and shows the predicted preorganization of the polymeric strands in the crystalline phase. © 2009 The Royal Society of Chemistry. 2009 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09599428_v19_n28_p4981_Chaia http://hdl.handle.net/20.500.12110/paper_09599428_v19_n28_p4981_Chaia |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Aliphatic chains Cl atoms Columnar mesophases Coordination Polymers Crystalline phase Crystallographic studies Dilatometry Diruthenium EXAFS Intermolecular space IR spectroscopy Lamellar mesophases Liquid-crystalline Liquid-crystalline phasis Local probes Magnetic susceptibility measurements Mesogenics Mesophases Mixed-valent Parallel arrangement Polarized optical microscopy Preorganization Resonance Raman Room temperature Structural arrangement Structural information Supramolecular architectures Thermal stability Variable temperature XRD Zig-zag Crystalline materials Differential scanning calorimetry Liquids Magnetic susceptibility Optical microscopy Ruthenium compounds X ray diffraction Polymers |
| spellingShingle |
Aliphatic chains Cl atoms Columnar mesophases Coordination Polymers Crystalline phase Crystallographic studies Dilatometry Diruthenium EXAFS Intermolecular space IR spectroscopy Lamellar mesophases Liquid-crystalline Liquid-crystalline phasis Local probes Magnetic susceptibility measurements Mesogenics Mesophases Mixed-valent Parallel arrangement Polarized optical microscopy Preorganization Resonance Raman Room temperature Structural arrangement Structural information Supramolecular architectures Thermal stability Variable temperature XRD Zig-zag Crystalline materials Differential scanning calorimetry Liquids Magnetic susceptibility Optical microscopy Ruthenium compounds X ray diffraction Polymers Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| topic_facet |
Aliphatic chains Cl atoms Columnar mesophases Coordination Polymers Crystalline phase Crystallographic studies Dilatometry Diruthenium EXAFS Intermolecular space IR spectroscopy Lamellar mesophases Liquid-crystalline Liquid-crystalline phasis Local probes Magnetic susceptibility measurements Mesogenics Mesophases Mixed-valent Parallel arrangement Polarized optical microscopy Preorganization Resonance Raman Room temperature Structural arrangement Structural information Supramolecular architectures Thermal stability Variable temperature XRD Zig-zag Crystalline materials Differential scanning calorimetry Liquids Magnetic susceptibility Optical microscopy Ruthenium compounds X ray diffraction Polymers |
| description |
Three series of mesogenic coordination polymers based on mixed-valent diruthenium tetracarboxylates, namely Ru 2 (3,4-B2OCn) 4 Cl, Ru 2 (3,5-B2OCn) 4 Cl and Ru 2 (3,4,5-B3OCn) 4 Cl [3,4-B2OCn = 3,4-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - , 3,5-B2OCn = 3,5-(C n H 2n+1 O) 2 C 6 H 3 CO 2 - and 3,4,5-B3OCn = 3,4,5-(C n H 2n+1 O) 3 C 6 H 2 CO 2 - ] have been synthesized and characterized, with the aim of obtaining columnar liquid crystalline phases. These equatorial BmOCn ligands have been selected under the assumption that they will efficiently fill the intermolecular space around the axial Cl atoms, thus warranting a parallel arrangement of the polymeric ⋯Ru 2 -Cl-Ru 2 -Cl⋯ strands in the crystalline phase, which should facilitate the occurrence of Col mesophases. The liquid crystalline character of the synthesized compounds has been studied by means of polarized optical microscopy, differential scanning calorimetry, and variable temperature X-ray diffraction. They all exhibit thermotropic Col H mesophases, the 3,4-B2OCn derivatives also exhibit a lamellar mesophase. Many of the studied compounds exhibit room temperature mesomorphism. The thermal stability domain of the Col H mesophases of the 3,5-B2OCn and 3,4,5-B3OCn derivatives is remarkably wide, from below 0 °C to ca. 300 °C in some cases. Based on pieces of structural information coming from XRD experiments, dilatometry, and local probes (magnetic susceptibility measurements, resonance Raman and IR spectroscopies, and Exafs) we suggest a model for the structural arrangement of the polymeric strands in the mesophase, in which the central polar backbone of the polymeric strands is in a zig-zag conformation, surrounded by a continuum of molten aliphatic chains. A crystallographic study of the non-mesogenic light homologue Ru 2 (3,4,5-B3OC2) 4 Cl confirms these aspects of the model, and shows the predicted preorganization of the polymeric strands in the crystalline phase. © 2009 The Royal Society of Chemistry. |
| title |
Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| title_short |
Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| title_full |
Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| title_fullStr |
Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| title_full_unstemmed |
Supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| title_sort |
supramolecular architecture elucidation of the room temperature columnar mesophases exhibited by mixed-valent diruthenium alkoxybenzoates |
| publishDate |
2009 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09599428_v19_n28_p4981_Chaia http://hdl.handle.net/20.500.12110/paper_09599428_v19_n28_p4981_Chaia |
| _version_ |
1768545984584876032 |