TRINUCLEAR METAL CHALCOGENIDE CLUSTERS AS PRECURSORS FOR SUPERATOMIC SOLIDS AND CLUSTER ORGANIC FRAMEWORKS
1 online resource (133 pages) : PDF
University of North Carolina at Charlotte
Inorganic molecular clusters Ni3(μ3-I)2(μ2-dppm)3 (1), Ni3(μ3-Te)2(μ2-dppm)3 (2), Ni3(μ3-Se)2(μ2-dppm)3 (3), Ni3(μ3-S)2(μ2-dppm)3 (4), Co4(μ3-S)4(PPri3)4 (5), and Mo3(μ3-S)2(μ2-S)3(PMe3)6 (6) have been used as building block precursors in the formation of binary superatomic solids with fullerenes (1-6•C60). These solids are crystallized from solution and charge transfer from the electron-rich molecular cluster precursors to fullerene was confirmed using infrared (IR) spectroscopy. Structural data for these superatomic solids was obtained using single-crystal X-ray diffraction (XRD) experiments and suggests that their assembly is directed by noncovalent interactions. Close-contacts, reminiscent of halogen bonds, between cluster capping ligands and fulleride anions are observed in the solid state. Superconducting quantum interference device (SQUID) magnetometry and two-probe conductivity measurements indicate that compounds 1•C60 and 2•C60 are paramagnetic and one hundred times more conductive than the constituent cluster precursors. Additionally, derivatives of molecular clusters 5 and 6 have been synthesized and investigated for use as superatomic secondary building units for 2D and 3D cluster organic frameworks. Characterization of these novel building blocks was accomplished using NMR spectroscopy as well as matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) and XRD analysis.
CLUSTER ORGANIC FRAMEWORKSFULLERIDESMETAL CHALCOGENIDE CLUSTERS
Rabinovich, DanielWalter, MichaelZhang, Yong
Thesis (M.S.)--University of North Carolina at Charlotte, 2017.
This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). For additional information, see http://rightsstatements.org/page/InC/1.0/.
Copyright is held by the author unless otherwise indicated.