Synthesis and properties of resorcin[4]arene based quadrupoles and dimeric electrostatic capsules
dc.contributor.author | Atkins, Joseph | |
dc.date.accessioned | 2009-05-11T15:46:28Z | |
dc.date.available | 2009-05-11T15:46:28Z | |
dc.date.graduationmonth | May | en |
dc.date.issued | 2009-05-11T15:46:28Z | |
dc.date.published | 2009 | en |
dc.description.abstract | In the present study, the rescorcin[4]arenes decorated with an alternating arrangement of pyridinium and sulfonate moieties were synthesized to establish a molecular quadrupole. These rescorcin[4]arenes are capable of undergoing conformational changes from a ‘collapsed’ to ‘open’ state. The stability of the two state are controlled by the polarity of the solvent environment. The electrostatic interactions between pyridinium and sulfonates enforced a ‘quadrupolar collapse’ in solvents such as chloroform. While these interactions are disrupted in dimethylsulfoxide. A major synthetic challenge was functionalizing the resorcin[4]arene in a positive/negative/positve/negative pattern was successfully addressed. Comparison to dipolar resorcin[4]arene were undertaken to establish a quantitative measurement of the quadrupolar forces and to address the question of cooperatively provided addition attraction beyond two dipoles. A,C-functionalized-bis sulfonate resorcin[4]arenes and A,C function bis-pyridinium resocin[4]arenes were synthesized independently. Combining these dicationic and dianionic moieties provided an interdigitating dimeric unit with overall quadrupolar charge distribution. Disruption of the quadrupolar salt bridges in CDCl[subscript]3 was accomplished through the addition of DMSO or through dilution. DeltaG[superscript]o, DeltaH[superscript]o, and DeltaS[superscript]o have been determined for the dimer formation. Addition of pyridinium salts led to a disruption of the dimeric capsule. Host-guest binding studies established attractive binding to CS[superscript]2. Larger guests such as toluene, diiodobenzene, dicynanobenzene could not be encapsulated. | en |
dc.description.advisor | Stefan Kraft | en |
dc.description.degree | Doctor of Philosophy | en |
dc.description.department | Department of Chemistry | en |
dc.description.level | Doctoral | en |
dc.identifier.uri | http://hdl.handle.net/2097/1398 | |
dc.language.iso | en_US | en |
dc.publisher | Kansas State University | en |
dc.subject | Cavitands | en |
dc.subject | Electrostatics | en |
dc.subject | Quadrupoles | en |
dc.subject | Capsule | en |
dc.subject.umi | Chemistry, Organic (0490) | en |
dc.title | Synthesis and properties of resorcin[4]arene based quadrupoles and dimeric electrostatic capsules | en |
dc.type | Dissertation | en |