B.S., Saint Mary's University (1994) Ph.D., University of Missouri-Columbia (1998) Research Associate, Steacie Institute for Molecular Sciences, National Research Council of Canada (1998-2000) Adjunct Research Professor, Ottawa-Carleton Chemistry Institute (1999-2000)

Organic Chemistry

Whereas more traditional approaches to chemical synthesis have focused upon atoms and molecules individually, our research encompasses understanding principles that govern the effects of intermolecular interactions (e.g. hydrogen bonds) on the structure and properties of assemblies of atoms and molecules in the field of supramolecular chemistry. The structure of DNA and ability of enzymes to catalyze chemical reactions are examples from biochemistry that are regulated by such interactions and we address whether such forces may be used to confront long-standing problems with new perspectives or design new molecules and materials with unique properties. Materials Design. It is well established that molecular approaches to crystal structure design can lead to new materials with desirable properties (e.g. optical). Despite this realization, an insufficient knowledge of factors that dictate crystal packing has hindered chemists from designing molecules that assemble to form functional solids, a priori, with predictable properties. This problem of crystal structure design, referred to as a problem of crystal engineering, is similar to solution phase organic synthesis in that chemists must plan routes, involving structural units known as synthons, to targeted, functional molecular systems. However, whereas solution phase organic synthesis is at a stage where synthetic routes are being reexamined to reduce steps for atom economy, the field of rational solid state design is at a stage where synthons are beginning to be identified. Of the properties that may be exploited for the design of molecular solids, it is solid state reactivity, in the form of bimolecular reactions, that we are studying. Such an approach to synthesis holds great promise for the designed, solvent-free synthesis of molecules, and materials, available either in low yields, as part of mixtures, or are completely inaccessible in the liquid phase. Unfortunately, however, most approaches to synthesis in the solid state are generally unreliable such that reaction homology, a concept central to the development of solution phase molecular synthesis, has been achieved with limited success. We are addressing this problem of reaction homology, using an approach that controls reactivity in solids by employing molecules that serve, via molecular recognition processes based on hydrogen bonds, as linear templates (see Figure 1), with the prospect that a reliable method for conducting reactions in the solid state will permit us to establish novel applications for the reactants (e.g. green chemistry), products (e.g. nanostructures), and materials (e.g. molecular devices). Figure 1. ORTEP perspectives of: (a) 2(resorcinol)·2(trans-1,2-bis(4-pyridyl)ethylene) and (b) 2(resorcinol)·rctt-tetrakis(4-pyridyl)cyclobutane. A photoinduced [2+2] cycloaddition in the solid state yields a cyclized product in which the diol directs formation of two covalent bonds by way of four O-H···N hydrogen bonds. With an interdisciplinary program that spans materials science and synthetic chemistry, students in our group are encouraged to face problems from a variety of perspectives, an approach that is becoming increasingly necessary as the lines between more traditional areas continue to be broken. Thus, in addition to developing synthetic methodologies, students, and other researchers, gain hands-on experience with state-of-the-art techniques of materials science (e.g. single-crystal X-ray analysis).

Sinnwell, M.A.; Baltrusaitis, J.; MacGillivray, L.R., "A Combination of Argentophilic and Perfluorophenyl-Perfluorophenyl Interactions Support a Head-to-Head [2+2] Photodimerization in the Solid State", Cryst. Grow. Des. 2015, 15, 538. Papaefstathiou, G.S.; Duncan, A.J.E.; MacGillivray, L.R., "Two act as one: unexpected dimers of catechol direct a solid-state [2+2] photodimerization in a six-component hydrogen-bonded assembly", ChemCommun. 2014, 50, 15960. Stojakovic, J.; Farris, B.S.; MacGillivray, L.R., "Liquid-assisted Vortex Grinding Supports the Single-step Solid-state Construction of a [2.2]Paracyclophane", Faraday Discuss. 2014, 170, 35-40. Bucar, D.-K.; Henry, R.F.; Zhang, G.G.Z.; MacGillivray, L.R., "Synthon Hierarchies in Crystal Forms Composed of Theophylline and Hydroxybenzoic acids: Cocrystal Screening via Solution-mediated Phase Transformation", Cryst. Grow. Des. 2014, 14, 5318. Hutchins, K.M.; Sumrak, J.C.; Swenson, D.C.; MacGillivray, L.R., "Head-to-tail Photodimerization of a Thiophene in a Co-crystal and a Rare Adipic Acid Dimer in the Presence of a Heterosynthon", CrystEngComm. 2014, 16, 5762-5764. Hutchins, K.; Rupasinghe, T.; Ditzler, L.; Swenson, D.; Sander, J.; Baltrusaitis, J.; Tivanski, A.; MacGillivray, L.R., "Nanocrystals of a Metal-Organic Complex Exhibit Remarkably High Conductivity that Increases in a Single-Crystal-to-Single-Crystal Transformation", J. Am. Chem. Soc. 2014, 136, 6778-6781. Hutchins, K.M.; Dutta, S.; Loren, B.P.; MacGillivray, L.R., "Co-crystals of a Salicylideneaniline: Photochromism Involving Planar Dihedral Angles", Chem. Mater. 2014, 26, 3042-3044. Elacqua, E.; Groeneman, R.H.; Reinheimer, E.W.; Bucar, D.-K.; MacGillivray, L.R., "Organosulfonates Aid Argentophilic Forces in the Crystal Engineering of [2+2] Photodimerizations: Reactivity Involving 3-Pyridyl Groups", Supramol. Chem. 2014, 26, 207-213. Laird, R.C.; Nguyen, N.P.; Rusch, S.; Baltrusaitis, J.; MacGillivray, L.R., "Bridging Electronic Behavior of Products of Click Reactions Manifested in the Solid State", Cryst. Grow. Des. 2014, 14, 893-896. Hutchins, K.M.; Sumrak, J.C.; MacGillivray, L.R.; "Resorcinol-Templated Head-to-Head Photodimerization of a Thiophene in the Solid State and Unusual Edge-to-Face Stacking in a Discrete Hydrogen-Bonded Assembly", Org. Lett. 2014, 16, 1052-1055. Bottorff, S.C.; Kasten, B.B.; Stojakovic, J.; Moore, A.L.; MacGillivray, L.R.; Benny, P.D., "Cu-free Click Reactions to Form Isoxazole Linkers in Chelating Ligands for fac-[MI(CO)3]+ Centers (M = Re, 99mTc)", Inorg. Chem. 2014, 53, 1943-1945. Bucar, D.-K.; Day, G.-M.; Halasz, I.; Zhang, G.G.Z.; Sander, J.R.G.; Reid, D.G.; MacGillivray, L.R.; Duera, M.J.; Jones, W., "The Curious Case of the (caffeine)∙(benzoic acid) Cocrystal: How Heteronuclear Seeding Transformed an Elusive Solid into a Long-lived One", Chem. Sci. 2013, 4, 4417-4425. Ghorai, S.; Sumrak, J.C.; Hutchins, K.M.; Bucar, D.-K.; Tivanski, A.V.; MacGillivray, L.R., "From Co-crystals to Functional Thin Films: Photolithography Using the [2+2] Photodimerization", Chem. Sci. 2013, 4, 4304-3408. Stojakovic, J.; Whitis, A.M.; MacGillivray, L.R., "Discrete Double-to-Quadruple Aromatic Stacks: Stepwise Integration of Face-to-Face Geometries in Cocrystals Based on Indolocarbazole", Angew. Chem., Int. Ed. 2013, 52, 12127-12130. Sander, J.R.G.; Bucar, D.-K.; Henry, R.F.; B.N.; Zhang, G.G.Z.; MacGillivray, L.R., "'Masked Synthons’ in Crystal Engineering: Insulated Components in Acetaminophen Cocrystal Hydrates", CrystEngComm., 2013, 15, 4816-4822. Bottorff, S.C.; Moore, A.L.; Wemple, A.R.; Bucar, D.-K.; MacGillivray, L.R.; Benny, P.D. "pH Controlled Coordination Mode Rearrangements of "Clickable" Huisgen based Multi-dentate Ligands with MI(CO)3+ (M = Re, 99mTc)", Inorg. Chem. 2013, 52, 2939-2950. Bhattacharya, S.; Stojakovic, J.; Saha, B.K.; MacGillivray, L.R., "A Product of a Templated Solid-State Photodimerization Acts as a Template: Single-Crystal Reactivity in a Single Polymorph of a Co-Crystal", Org. Lett. 2013, 15, 744-747. Dutta, S.; Bucar, D.-K.; Elacqua, E.; MacGillivray L.R., "Single-Crystal-to-Single-Crystal Direct Cross-linking and Photopolymerisation of a Discrete Ag(I) Complex to Give a 1D Polycyclobutane Coordination Polymer", ChemCommun. 2013, 49, 1064-1066. Friscic, T.; Varshney, D.B.; Elacqua, E.; Sumrak, J.C.; Sokolov, A. N.; MacGillivray, L.R. "Molecular Self-Assemblies in Co-Crystals: Engineering Chemical Reactivity and Organic Semiconductor Materials", in Molecular Self-Assembly: Advances and Application (Pan Stanford Publishing, 2013), 223-238 (invited book chapter). Elacqua, E.; Bucar, D.-K.; Henry, R.F.; Zhang, G.G.Z.; MacGillivray, L.R., "Supramolecular Complexes of Sulfadiazine and Pyridines: Reconfigurable Exteriors and Chameleon-like Behavior of Tautomers at the Co-crystal - Salt Boundary", Cryst. Grow. Des. 2013, 13, 393-403.