Balancing intermolecular interactions in the design and synthesis of supermolecules

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dc.contributor.author Schultheiss, Nathan C.
dc.date.accessioned 2007-04-16T15:13:17Z
dc.date.available 2007-04-16T15:13:17Z
dc.date.issued 2007-04-16T15:13:17Z
dc.date.submitted May 2007 en
dc.identifier.uri http://hdl.handle.net/2097/264
dc.description.abstract The directed-assembly of small molecular building-blocks into discrete supermolecules or extended networks through non-covalent intermolecular interactions is an on-going challenge in the field of crystal engineering. This synthetic challenge may be overcome by identifying or establishing a hierarchy of intermolecular interactions which, in turn, may facilitate a modular supramolecular assembly process producing final products in high yields. A family of three 3-pyridine/amino-pyrimidine supramolecular reactants (SR’s) was prepared and allowed to react with aromatic carboxylic acids producing nine 1:1 molecular co-crystals and four 1:1 ionic salts through heteromeric O-H···N/N-H···O or charge-assisted N–H+···O-/N–H···O- hydrogen bonds with the amino-pyrimidine binding site. We introduced a Q-value, based on AM1 calculations, to show that the amino-pyrimidine moiety is a superior hydrogen-bond acceptor for an incoming carboxylic acid. The amino-pyrimidine/carboxylic acid synthon resulted 13/13 times (100 % yield) even in the presence of other potentially disruptive intermolecular interactions. However, reacting a 4-pyridine/amino-pyrimidine SR and a carboxylic acid in a 1:2 ratio, resulted in structures containing both acid/amino-pyrimidine and acid/pyridine synthons. The same family of pyridine/amino-pyrimidine SR’s were allowed to react with halogentated benzoic acids in which the amino-pyrimidine/carboxylic acid synthon formed 7/7 times (100 % yield) and halogen bonds (N···I or N···Br) extended the SR/acid dimers into polymeric networks 4/7 times (57 %). These results were rationalized through a hierarchial view of intermolecular interactions consisting of hydrogen and halogen bonds. Four bifunctional 3-pyridine/amino-pyrimidine or amino-pyridine SR’s were reacted with neutral metal complexes producing thirteen crystal structures in which the pyridyl moiety coordinates to the metal center 13/13 times (100 % yield) and amino-pyrimidine···amino-pyrimidine hydrogen bonds link the neighboring metal-ligand complexes 10/13 times (77 % yield) into 1-D or 2-D extended architectures. Finally, we synthesized and characterized a series of tetra-substituted hydrogen bond donor and acceptor functionalized, i.e. pyridyl, amino-pyridine, carboxylic acid, resorcinarene-based cavitands forming deep-walled cavitands through amino-pyridine···carboxylic acid heteromeric synthons and a heterodimeric molecular capsule through pyridyl···carboxylic acid hydrogen bonds. The heterodimeric capsule is only one of three, of its type, characterized crystallographically. en
dc.language.iso en_US en
dc.publisher Kansas State University en
dc.subject Supramolecular Chemistry en
dc.subject Hydrogen bonds en
dc.title Balancing intermolecular interactions in the design and synthesis of supermolecules en
dc.type Dissertation en
dc.description.degree Doctor of Philosophy en
dc.description.level Doctoral en
dc.description.department Department of Chemistry en
dc.description.advisor Christer B. Aakeroy en
dc.subject.umi Chemistry, Inorganic (0488) en
dc.subject.umi Chemistry, Organic (0490) en
dc.date.published 2007 en
dc.date.graduationmonth May en

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