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Heterobimetallic lantern complexes: intermolecular properties and utility as a monodentate ligandBeach-Molony, Stephanie Ann 24 January 2021 (has links)
A family of new [PtM(SAc)4(pySMe)] (M = Mn (42), Fe (43), Co (44), Ni (45), Zn (46)) lanterns and an expansion of the [PtM(SAc)4(pyNH2)] family to include M = Mn (47) and Fe (48) lanterns have been synthesized and their detailed structural and magnetic characterization are reported. Compounds 43-45 have been found to contain exceptionally long Pt…Pt metallophilic contacts with antiferromagnetic coupling across the staggered dimers in the solid state.
The utility of the [PtVO(SOCR)4] lanterns as monodentate, terminal oxo-bound ligands is proven in the formation of trimetallic lanthanide complexes [Ln(ODtbp)3{PtVO(SOCR)4}] (Ln = Ce, R = Me (49); Ln = Ce, R = Ph (50); Ln = Nd, R = Me (51); Ln = Nd, R = Ph (52)). Structural and magnetic studies are reported of the four, four-coordinate lanthanide complexes. All four complexes were found to exhibit antiferromagnetic coupling between the 3d-4f ions, the strongest of which is observed in 50. Through AC magnetic susceptibility studies,
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SMM behavior was also observed in all four complexes, with the slowest relaxation found in 52.
A pair of [PtNi(SAc)4(L)] (L = pyCN (54), HpipCN (55)) and new {S,N} chelated mercaptopyridine lanterns [PtNi(mpyS)4(L)] (L = H2O (56), MeCN (57), pyCN (58)) have been synthesized and a detailed structural comparison of the systems made. The stronger field mercaptopyridine ligand is shown to decrease the Pt (donor) – M (acceptor) character within the lantern, reducing the Pt(II) Lewis acidity and therefore preventing the formation of intermolecular interactions in Ni(II) complexes 56-58. Additionally, the development of an improved air- and water-stable synthesis for the formation of the di-Pt mercaptopyridine para-hydro lantern, [Pt2(pyS)4], is reported along with its previously unknown crystal structure.
In an attempt to make a diamagnetic [PtZn(mpyS)4(L)] analog to the previous Ni(II) mercaptopyridine lanterns, a new series of {PtnZn2} HEMACs has been discovered and structurally characterized with n = 1, 2, 3,. The discovery of a trimetallic {Pt(IV)Zn2} (60) para-methyl mercaptopyridine bridged complex with novel {Pt(IV)S6} ligation is discussed. The use of para-H substituted mercaptopyridine led to insoluble tetranuclear {Pt2Zn2} (61) while use of the para-methyl substituted ligand led to the insoluble pentanuclear {Pt3Zn2} (62) through solvothermal syntheses.
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The Synthesis of Inorganic Paddlewheel and Iron-Sulfur Complexes in Reduced Oxidation StatesScott, Thomas A. 14 July 2006 (has links)
No description available.
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Synthesis of Bimetallic Paddlewheel Complexes and Metal Organic Frameworks for Future Use in CatalysisMattox, Tracy Marie 30 November 2006 (has links)
No description available.
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Synthesis and Characterization of Three New Tetrakis(N-phenylacetamidato) Dirhodium(II) Nitrile ComplexesAtem-Tambe, Nkongho 01 December 2013 (has links)
Three new tetrakis [Rh2(PhNCOCH3)4·xNCR] (R = {2-CH3}C6H4 (x=2), R = {3-CH3}C6H4 (x=1), R = (3-CN)C6H4∞ (x=1)) complexes have been synthesized and characterized. These complexes were characterized by IR and 1H NMR spectroscopies and X-ray crystallography which solved with R1<0.05.
[Rh2(PhNCOCH3)4·2NC{2-CH3}C6H4] was triclinic (a=9.79Å, b=14.79Å, c=16.36Å, α=103.84⁰, β=99.17⁰, γ=99.77⁰, P-1(#2), μCN=2227.78cm-1, Rh-Rh=2.42Å, N-C=1.13Å, 1.14Å, Rh-N=2.34Å, 2.35Å, Rh-N-C=151.6⁰, 152.5⁰, Rh-Rh-N=173.0⁰, 174.6⁰).
[Rh2(PhNCOCH3)4·NC{3-CH3}C6H4] was triclinic (a=11.71Å, b=13.02Å, c=13.40Å, α=72.34⁰, β=66.78⁰, γ=82.74⁰, P-1(#2), μCN=2241.28cm-1, Rh-Rh=2.40Å, N-C=1.14Å, Rh-N=2.16Å, Rh-N-C=166.3⁰, Rh-Rh-N=175.9⁰).
[Rh2(PhNCOCH3)4·2NC{3-CN}C6H4]∞ was triclinic (a=11.88Å, b=13.30Å, c=14.88Å, α=77.98⁰, β=74.61⁰, γ=65.48⁰, P-1(#2), μCN=2233.57cm-1, Rh-Rh=2.41Å, N-C=1.13Å, 1.13Å, Rh-N=2.18Å, 2.38Å, Rh-N-C=166.8⁰, 127.7⁰, Rh-Rh-N=178.4⁰, 175.4⁰).
The bond distances, bond angles and bonding interactions (σ and π) are similar to the metal-carbene bond formed during carbenoid transformations catalyzed by dirhodium(II) compounds.
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Synthesis of Heterobimetallic Clusters and Coordination Networks via Hard-Soft InteractionsCollins, David J. 29 April 2008 (has links)
No description available.
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Structural Diversity in Metal-Organic Nanoscale Supramolecular ArchitecturesAbourahma, Heba 04 April 2004 (has links)
Supramolecular synthesis has gained much attention in recent years. Such an approach to synthesis represents an attractive alternative to traditional, multi-step synthesis, especially for making complex, nanoscopic structures. Of particular interest, in the context of this work, is the use of metal-organic interactions to direct the self-assembly of nanoscopic architectures. These interactions are highly directional, relatively "strong" (compared to other supramolecular interactions) and kinetically labile, which allows for "self-correction" and in turn the production, often in high yield, of defect-free products. This also means that a number of related, yet structurally diverse products (supramolecular isomers) could be isolated.
The work presented herein demonstrates the supramolecular synthesis of related, yet structurally diverse family of metal-organic nanoscale supramolecular architectures that are based on the ubiquitous paddle-wheel dimetal tetracarboxylate secondary building unit (SBU) and angular dicarboxylate ligands. It also demonstrates that the SBU self-assembles into clusters of four (tetragonal) and three (trigonal) nanoscale secondary building units (nSBU), which further self-assemble into nanoscale structures that include discrete (0D) faceted polyhedra, tetragonal 2D sheets and another 2D sheet that conforms to the so-called Kagom lattice. In addition, the work herein demonstrates that synthesis under thermodynamic equilibrium conditions facilitates "self-correction" so that the most stable thermodynamic product is obtained. Synthesis, characterization and crystal structure analysis of these structures is presented herein.
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Charge Distribution in the MLCT States of <i>trans</i>-M<sub>2</sub>L<sub>2</sub>L’<sub>2</sub> and M<sub>2</sub>L<sub>4</sub> Compounds Studied by Femtosecond Spectroscopy, where M= Mo and WJiang, Changcheng January 2016 (has links)
No description available.
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Heteroleptic paddlewheel complexes and molecular assemblies of dimolybdenum and ditungsten: A study of electronic and structural controlBrown, Douglas J. 14 September 2006 (has links)
No description available.
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EVALUATION OF SINGLE MOLECULE DIODES FABRICATED VIA ELECTRON-BEAM LITHOGRAPHY AND METAL-ORGANIC FRAMEWORKS INCORPORATING TWO NOVEL LIGANDS, A TRIGONAL PLANAR CARBOXYLATE LIGAND AND A TETRAHEDRAL TETRAZOLATE-BASED LIGANDUrig, Christina S. 17 April 2007 (has links)
No description available.
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Photophysical and Photosensitizing Properties of Dimetal Quadruply Bonded Paddlewheel Complexes Probed Through Ultrafast SpectroscopyBrown-Xu, Samantha E. 10 October 2014 (has links)
No description available.
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