TRINUCLEAR METAL CHALCOGENIDE CLUSTERS AS PRECURSORS FOR SUPERATOMIC SOLIDS AND CLUSTER ORGANIC FRAMEWORKS

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Shott, J. (2017). TRINUCLEAR METAL CHALCOGENIDE CLUSTERS AS PRECURSORS FOR SUPERATOMIC SOLIDS AND CLUSTER ORGANIC FRAMEWORKS. Unc Charlotte Electronic Theses And Dissertations.
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Abstract

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.

Details
Author

Shott, Jessica

Title

TRINUCLEAR METAL CHALCOGENIDE CLUSTERS AS PRECURSORS FOR SUPERATOMIC SOLIDS AND CLUSTER ORGANIC FRAMEWORKS

Physical Description

1 online resource (133 pages) : PDF

Date

2017

Degree Granting Institution

University of North Carolina at Charlotte

Abstract

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.

Genre

masters theses

Subjects--Topics

Nanoscience
Chemistry
Chemistry, Inorganic

Degree

M.S.

Keywords

Cluster Organic Frameworks
Fullerides
Metal Chalcogenide Clusters

Subject Area

Chemistry

Advisor(s)

Bejger, Christopher

Committee Members

Rabinovich, Daniel
Walter, Michael
Zhang, Yong

Degree Note

Thesis (M.S.)--University of North Carolina at Charlotte, 2017.

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Rights Holder Information

Copyright is held by the author unless otherwise indicated.

Identifier

Shott_uncc_0694N_11419

Permalink

http://hdl.handle.net/20.500.13093/etd:371