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Investigations Into Ligand Substitutions Of Rhenium And Molybdenum D4 Hexanuclear Clusters And The Synthesis And Characterization Of Aurated Pyrene And Thiophene Derivatives
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Book Synopsis Investigations Into Ligand Substitutions of Rhenium and Molybdenum D^4 Hexanuclear Clusters and the Synthesis and Characterization of Aurated Pyrene and Thiophene Derivatives by : Miya Alethea Peay
Download or read book Investigations Into Ligand Substitutions of Rhenium and Molybdenum D^4 Hexanuclear Clusters and the Synthesis and Characterization of Aurated Pyrene and Thiophene Derivatives written by Miya Alethea Peay and published by . This book was released on 2011 with total page 201 pages. Available in PDF, EPUB and Kindle. Book excerpt: Ligand substitution reactions were performed on d 4 rhenium and molybdenum hexanuclear clusters. For the [Re6(3-Q)8] 2+ clusters, where Q= S, Se, varying amounts of tributylphosphine and reaction times yielded multiply substituted clusters. Phosphine substituted reactions were monitored by 31P and 1H NMR as well as mass spectrometry. 31P NMR showed substitution through downfield shifts, for the [Re6S8] 2 clusters, and upfield for that of the [Re6Se8] 2+ clusters from the free tributylphosphine ligand, while mass spectrometry determined the amount of bound phosphines (four or five). Cis-, trans-, and penta-phosphine clusters were generated from these reactions. Triflates replaced apical chlorides on the Mo(II) cluster for increasing lability. A crystal structure was determined from this cluster displaying that of a [Mo6Cl8] 4 core surrounded by six triflate ligands bound through oxygen. Two tetraphenylphosphonium cations are also found with the structure. Base-promoted transmetalation was used to attach phosphine gold(I) fragments to the ends of pyrene. Three new compounds were generated with tricyclohexylphosphine- and triphenylphosphinegold(I) at the 2- and 2,7-positions. 31P and 1H NMR confirm reactions went to completion with no traces of the starting phosphine. Diffraction quality crystals were reported for two of the products. Binding of the phosphine causes a red shifting and increase of the absorbance which is further enhanced with additional gold(I) ligands. Finally, diaurated bithiophene was produced from a boron transmetalation reaction. Triphenylphosphinegold bromide provided a suitable starting ligand for the replacement of terminal boropinacolates on the bithiophene. Reaction monitoring through multinuclear spectroscopy and mass spectrometry determined a diaurated species. A crystal structure allowed visual confirmation of the complex demonstrating the triphenylphosphinegold(I) ligand bound to the carbon adjacent to the sulfur atom. In agreement with aurated pyrenes, phosphine binding both red shifts and increases the absorbance. Further evaluation would enable studies of its optoelectronics properties.
Book Synopsis Progress Towards the Synthesis of Site-differentiated Hexanuclear Molybdenum and Rhenium Clusters Containing Sulfur Donor Ligands by : Jeffrey N. Templeton
Download or read book Progress Towards the Synthesis of Site-differentiated Hexanuclear Molybdenum and Rhenium Clusters Containing Sulfur Donor Ligands written by Jeffrey N. Templeton and published by . This book was released on 2006 with total page 230 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis and Characterization of Hexanuclear Rhenium Chalcogenide Clusters Containing Potential Two-Photon Absorbing Ligands and the Synthesis and Characterization of Gold-Substituted Coumarins by : James Benjamin Updegraff (III.)
Download or read book Synthesis and Characterization of Hexanuclear Rhenium Chalcogenide Clusters Containing Potential Two-Photon Absorbing Ligands and the Synthesis and Characterization of Gold-Substituted Coumarins written by James Benjamin Updegraff (III.) and published by . This book was released on 2010 with total page 182 pages. Available in PDF, EPUB and Kindle. Book excerpt: Hexanuclear rhenium clusters of the form Re6(u^3-Q8)(PR3)4X2, (Q = Se, S and X = Br- or I- ), and Re6(u^3-Q8)(PR3)4(PEt3)2, where PR3 = tris(4-(4-tert-butylstyrenyl)phenyl)phosphine (PTbs3) have been synthesized and characterized. PTbs3 was chosen for its potential as a two-photon absorbing ligand. Binding of PTbs3 to the cluster core does not completely quench the luminescence of the cluster core. The requirements for Förster energy transfer (FRET) have also been fulfilled. Accessing to the triplet state emission of the cluster core by exciting the PTbs3 ligand using lower-energy light should be achieved. Coumarins substituted at the 6-, 7-, and 8-positions with (phosphine/carbene)gold(I) fragments have also been synthesized in an effort to probe the luminescent properties brought about by a heavy atom such as gold. Each new substituted-coumarin has been characterized by multi-nuclear NMR, elemental combustion analysis, UV-Vis spectroscopy and emissions spectroscopy. In each case, the addition of the gold(I) fragment resulted in the observance of triplet-state emission at room temperature which was not observed for the free coumarin molecule.
Book Synopsis Synthesis, Characterization, and Reactivity of Hexanuclear Rhenium Clusters Containing Nitrogen-donor Ligands by : Jessica L. Durham
Download or read book Synthesis, Characterization, and Reactivity of Hexanuclear Rhenium Clusters Containing Nitrogen-donor Ligands written by Jessica L. Durham and published by . This book was released on 2012 with total page 214 pages. Available in PDF, EPUB and Kindle. Book excerpt: