Molecular Magnetism: The Design, Synthesis, and Characterization of New Building Blocks for Molecule-based Magnetic Materials

Two classes of building blocks have been prepared and characterized and their coordination chemistry explored working towards the preparation of new molecule-based magnetic materials. In the first project, the amine functionality of 3,3'-diamino-2,2'- bipyridine was exploited for the preparation of a new family of ligands (H2L 1)-(H2L 4). The molecular structures of three ligands have been fully characterized by X-ray crystallography. [molecular structure diagram will not copy here, but is available in full pdf.] The coordination chemistry of these ligands with divalent first row transition metal ions was investigated. For ligand (H2L1), the molecular structures of four coordination complexes with stoichiometries [Zn2(Ll)(OAc)(MeO)]2 (I), [Cu2(L1)(OAc)2 (II), [Li(L1)]3 (III), and [Ni(L1)]3 (IV) were determined by X-ray crystallography. For ligand (H2L2), a Cu(II) complex of stoichiometry [Cu3(L2)(OAc)3MeO] (V) was determined by X-ray crystallography. The magnetic properties of complexes (II), (III), and (V) have been fully elucidated. In project two, synthetic strategies for the preparation of porphyrin molecules bearing triol substituents is presented. Following this approach, three new porphyrin derivatives have been prepared and characterized [Zn(HPTPP-CH2C(CH20H)3)] (VI), [P(TPP)(OCH2C(CH2)H)3)2]+CL- (VII), and [P(OEP)(C6H5)(OCH2C(CH2OH)3)]+Cl- (VIII). Attempts to exchange the labile methoxide bridges of a tetraironIIl single molecule magnet of stoichiometry [Fe4(OMe)6(dpm)6] (Hdpm = dipivaloylmethane) with the triol appended porphyrins will be discussed. [molecular structure diagram will not copy here, but is available in full pdf.]

Ligand design for molecule-based magnetic and/or conducting materials

Work in the area of molecule-based magnetic and/or conducting materials is presented in two projects. The first project describes the use of 4,4’-bipyridine as a scaffold for the preparation of a new family of tetracarboxamide ligands. Four new ligands I-III have been prepared and characterized and the coordination chemistry of these ligands is presented. This project was then extended to exploit 4,4’-bipyridine as a covalent linker between two N3O2 macrocyles. In this respect, three dimeric macrocycles have been prepared IV-VI. Substitution of the labile axial ligands of the Co(II) complex IV by [Fe(CN)6]4- afforded the self-assembly of the 1-D polymeric chain {[Co(N3O2)H2O]2Fe(CN)6}n•3H2O that has been structurally and magnetically characterized. Magnetic studies on the Fe(II) complexes V and VI indicate that they undergo incomplete spin crossover transitions in the solid state. Strategies for the preparation of chiral spin crossover N3O2 macrocycles are discussed and the synthesis of the novel chiral Fe(II) macrocyclic complex VII is reported. Magnetic susceptibility and Mössbauer studies reveal that this complex undergoes a gradual spin crossover in the solid state with no thermal hysteresis. Variable temperature X-ray diffraction studies on single crystals of VII reveal interesting structural changes in the coordination geometry of the macrocycle accompanying its SCO transition. The second project reports the synthesis and characterization of a new family of tetrathiafulvalene derivatives VIII – XII, where a heterocyclic chelating ligand is appended to a TTF donor via an imine linker. The coordination chemistries of these ligands with M(hfac)2.H2O (M( = Co, Ni, Mn, Cu) have been explored and the structural and magnetic properties of these complexes are described.

Donald Ziraldo Fonds, 1968-2012, n.d.

Donald J. P. Ziraldo, C.M., BSc., LLD was born in St. Catharines, Ontario on October 13, 1948 to Fredrick and Irma (Schiratti) Ziraldo. He graduated Denis Morris High School in St. Catharines in 1967, and received his B.Sc. in Agriculture at the University of Guelph in 1971. In 1974, Ziraldo was running Ziraldo Nurseries when he met Austrian born schoolteacher, chemist and winemaker Karl J. Kaiser. They realized that there was a gap in the premium varietal wine market and decided to plant a premium traditional European variety of grape vine species, the Vitis vinifera. This was an innovation in the Niagara region because the current wine producers were not using premium European grapes at the time. Ziraldo and Kaiser founded and then formally incorporated Inniskillin Wines Inc. in Niagara-on-the-Lake, Ontario on July 31, 1975. Ziraldo successfully lobbied General George Kitching, CEO of the LCBO, for a winery license. In 1975, Kitching granted him a winery license, the first in Ontario since Prohibition ended. From the beginning, there was a division of labour where Kaiser focused on the winemaking and Ziraldo focused on the marketing and promotion of the wines. Ziraldo also became president of the company. Ziraldo and Kaiser worked on improving their winemaking techniques and promoting their products and company. Ziraldo has been called ‘one of the founding fathers of the Canadian wine industry’, and it is widely acknowledged that both men played a large role in the success and growth of the Canadian wine industry. Together they pioneered the estate winery movement in Canada. A major turning point Inniskillin came in 1984 when Karl Kaiser successfully harvested the first Icewine crop from frozen grapes on the vine and bottled Eiswein Vidal (Icewine). In 1990, Inniskillin received worldwide recognition for this Icewine when their 1989 Vidal Icewine won the most prestigious award in the wine world, the Grand Prix d’Honneur, given at Vinexpo in France. This victory has been called ‘the award heard round the world’ and it launched Inniskillin into the international wine arena. At the same time, this helped lift the profile of Canadian wines in general. Inniskillin not only became Canada’s leading producer of Icewine, but it also became known for producing ‘one of the world’s great wines’. After the 1990 award, Ziraldo began a major public relations campaign to promote Inniskillin and build Icewine into a worldwide brand. He travelled broadly every year to promote the brand and products and networked extensively with politicians, celebrities, chefs, sommeliers, etc. To ensure worldwide and long-term success, Ziraldo introduced Icewine to Asia and the United States which were new markets. He developed a new Icewine glass with George Riedel. Tony Aspler has called Ziraldo ‘Canada’s Wine Ambassador’. Ziraldo was President of Inniskillin Wines Inc. (Niagara) from 1975 to 2006. In 1992, Inniskillin merged with Cartier Wines, and in 1993 Cartier Inniskillin Vintners Inc. merged with T.G. Bright & Co. Limited, forming the new company Vincor International Inc. Inniskillin wines was now a subsidiary of Vincor. Ziraldo became a Director at Vincor International Inc. from 1993 to 2004. From 1989 to the mid 1990s, Ziraldo also became President of Inniskillin Napa, in Napa Valley, California. Inniskillin purchased Napa Valley vineyards and produced wines under the Terra label. In 1994, Ziraldo set up a subsidiary estate winery of Inniskillin in Oliver, British Columbia which was called Inniskillin Okanagan Vineyards Inc. He became President of the winery. This started as a partnership between Inniskillin and the local Inkameep Indian Band in the Okanagan. In 2006, Ziraldo left Inniskillin and since that time he has been involved in other Icewine related ventures such as running Ziraldo Estate Winery and producing Ziraldo Riesling Icewine 2007. He also is in partnership with the Niagara based Equifera Estate Winery to produce Equifera Icewine. His most recent projects include planting Picolit grapes in his parent’s hometown, in a project called Picolit Di Fagagna and becoming Managing Director of the Senhora Do Convento Port Winery in Portugal. Donald Ziraldo was instrumental in the creation of the Vintners Quality Alliance (VQA) in Ontario and was its founding Chair from 1988-1995. The VQA was established as a regulatory and appellation system which secured the quality and origin of Canadian wines made under this system. The VQA designation and bottle label gave the consumer confidence that the wines they were purchasing were 100% local products. The VQA system was set up first in Ontario and then in British Columbia.