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, xii 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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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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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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