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.
| Identifer | oai:union.ndltd.org:bu.edu/oai:open.bu.edu:2144/41904 |
| Date | 24 January 2021 |
| Creators | Beach-Molony, Stephanie Ann |
| Contributors | Doerrer, Linda H. |
| Source Sets | Boston University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis/Dissertation |
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