Following an overview on the progress so far made in the general area of calixarene chemistry, this thesis reports investigations related to i) the acid-base properties of p-tert-butycalix[n]arenes (n=4,6,8) and amines (trimethylamine, tert-butylamine, atropine, 1-aminoadmantane, morpholine, R-(+)-alpha-methylbenzylamine, piperazine, cryptands 22 and 222) in benzonitrile at 298.15 K and their implications on the proton transfer reaction from the calixarene to the amine. Fom experimental data, the individual processes which contribute to the overall extraction of tert-butylamine from water by p-tert-butylcalix[8]arene in benzonitrile were quantitatively assessed. ii) the use of phase transfer catalysis for the synthesis of ethy p-tert-butycalix[n]arene (n=4,6,8) ethanoates. Advantages with respect to current preparative methods are outlined. The stability constant of sodium and ethyl p-tert-butylcalix[4]arene tetraethanoate in acetonitrile at 298.15 K was determined by direct potentiometry using an ion-selective electrode. The result obtained, is in good agreement with that recently reported from a double competitive potentiometric method. Extraction data in the water-benzonitrile solvent system at 298.15 K were used to quantitatively evaluate for the first time the individual processes involved in the overall extraction of alkali-metal picrates by ethy p-tert-butycalix[4]arene tetraethanoate. iii) the synthesis and characterization of new calixarene derivatives obtained by the lower rim functionalization of p-tert-butycalixarense by the introduction of a) N,N-dimethylcarbamoyl and N-acetylglycine groups using phase transfer catalysts (18-crown-6,4- dimethylaminopyridine and 1,3-dicyclohexylcarbodiimide). In both cases, disubstituted calixarene derivatives were obtained in distorted cone conformations, b) aliphatic (methyl, ethyl, isopropyl), alicyclic (piperidine, pyrrolidine, morpholine) and aromatic (quinoline, pyridine) amino groups. These were characterized by elemental analysis, 1H and 13C NMR spectroscopy. The acid-base properties of these derivatives were investigated in methanol. The ability of these ligands in their neutral and protonated forms to interact with cations and anions; respectively, is discussed. Final conclusions of these investigations are summarized and suggestions for further work are given.

In the present thesis, both the published and the "ready-to-be-submitted" results concerning electrochemistry of calixarenes are summarized. The main focus is given to the detailed interpretation of experimental data, acquired during a systematic study of electroactive calixarene derivatives. The experiments were conducted under aprotic conditions (DMF) on mercury electrodes (mainly cyclic voltammetry and DC-polarography). It is demonstrated that electrochemistry should not serve only for redox characterization of studied compounds, but it offers a great number of other valuable information. The subject matter of the study are the calix[4]arenes (prevalently in the cone-conformation) which bear one to four reducible or oxidizable substituents ("redox probes") at various positions in order to be electrochemically investigable. Nitro- and nitroso compounds together with aldehydes, ketones, nitriles, aldoximes, carboxylic acids and corresponding esters, sulphones and esters of sulphonic acids are the most discussed compound series. Their relationship between structure and electrochemical response is presented in new connections ("stereoelectrochemistry"), in other words, how the redox probe position on the benzene ring (para-/meta-), bridging groups, or adjacent vs. opposite aromatic units...

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We have investigated the use of calix[4]arenes in 3d and 3d/4f chemistry which produced a family of 7 new complexes. These are: [MnIII2MnII2(OH)2(TBC4)2(DMF)6] (1) , the analogous version with C4 (2). [MnIII4GdIII4(OH)4(C4)4(NO3)2(DMF)6(H2O)6](OH)2 (3), [MnIII4TbIII4(OH)4(C4)4(NO3)2(DMF)6(H2O)6](OH)2 (4), [MnIII4DyIII4(OH)4(C4)4(NO3)2(DMF)6(H2O)6](OH)2 (5), [CuII9(OH)3(TBC4)3Cl2(DMSO)6](CuICl2)·DMSO (6·DMSO) (6) and [CuII9(OH)3(TBC4)3(NO3)2(DMSO)6](NO3)· DMSO (7·DMSO) (7). We continued with a series of Pseudo Metallocalix[6]arene planar disc complexes : [Ni7(OH)6(L1)6](NO3)2 (8), [Ni7(OH)6(L1)6](NO3)2.2MeOH (9), [Ni7(OH)6(L1)6](NO3)2.3MeNO2 (10), [Ni7(OH)6(L2)6](NO3)2.2MeCN (11), [Zn7(OH)6(L1)6](NO3)2.2MeOH.H2O (12) and [Zn7(OH)6(L1)6](NO3)2.3MeNO2 (13) and in the final part of this thesis we present a family of tetranuclear mixed valent Mn complexes using the tripodal ligand heedH2 : [MnII2MnIV2O2(heed)2(EtOH)6Br2]Br2 (14), [MnII2MnIV2O2(heed)2(H2O)2Cl4] (15), [MnII2MnIV2O2(heed)2(heedH2)2](ClO4)4 (16), [MnII2MnIV2O2(heed)2(MeCN)2(H2O)2(bpy)2](ClO4)4 (17), [MnII2MnIV2O2(heed)2(bpy)2Br4] (18); and the 2-D network of tetranuclear MnII/IV clusters {[MnII2MnIV2O2(heed)2(H2O)2(MeOH)2(dca)2]Br2}n (19). In total nineteen new complexes are reported. Studies of the magnetic properties show that 1 and 2 are SMM’s, whilst complex 3 is an excellent magnetic refrigerant for low-temperature applications and 4 and 5 behave as low-temperature molecular magnets.

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Thesis (Ph. D.)--Texas Christian University, 2009. / Title from dissertation title page (viewed Oct. 30, 2009). Includes abstract. Includes bibliographical references.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005. / Shuker, Suzanne, Committee Chair ; Seley, Katherine, Committee Member ; DeWeerth, Steve, Committee Member ; Doyle, Donald, Committee Member ; Collard, David, Committee Member. Vita. Includes bibliographical references.

Thesis (Ph.D.)--University of Western Australia, 2008.

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