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Title: Host and metallo-supramolecular chemistry of cyclotriveratrylene based molecules
Author: Little, Marc Adrian
Awarding Body: University of Leeds
Current Institution: University of Leeds
Date of Award: 2012
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The novel thiolated cyclotriveratrylene based molecule cyclotrithiophenolene, 2.8 was synthesised from cyclotriphenolene in three steps. Compound 2.8 undergoes dimerisation via disulfide bond formation to the anti-disulfide linked S-cryptophane 0.0.0 2.10, preferentially over the syn-disulfide linked S-cryptophane 0.0.0 2.9. The host properties of compound 2.10 have been investigated in the presence of a number of gaseous guests including methane and nitrogen. The methoxy analogue of compound 2.8, namely cyclotrithioguaiacylene 2.3, does not undergo selective dimerisation to the desired disulfide linked cryptophane. The proposed explanation for this is due to steric clashes between the methoxy groups. Novel 10 and 20 coordination polymers or discrete coordination complexes have been prepared with previously reported cyclotriguaiacylene-type ligands tris-[4-(3- pyridyl)benzoyl]cyclotriguaiacylene L3.1, tris-[4-(4-pyridyl)benzoyl]cyclotriguaiacylene L3.2, tris-[3-(3-pyridyl)benzoyl]cyclotriguaiacylene L3.3, tris-[4-(3,5- pyrimidyl)benzoyl]cyclotriguaiacylene L3.4, and novel tris-[3-(3-pyridyl-4- benzyl)benzoyl]cyclotriguaiacylene L3.5. Complexes include: the discrete anti-metallo- cryptophane [M3(L3.1 MN03)s] where M = Zn 3.1, M = Cd 3.2; the discrete coordination complex [Nis(L3.3MOAc)g(OHMOH2h].(OAc).2(NMP).2(H20) 3.7 (where NMP = N- methylpyrrolidone); the 10 networks [Cd2(L3.2)(N03h(H20MOMAh].(N03).4(OMA) 3.3 (where OMA = dimethylacetamide) [Zn(L3.2MCF3COO)(H20)].(CF3COO).7(NMP) 3.5 and [Co(L3.3)(N03h].4(NMP) 3.6; the 20 network [Cd2(L3.2MN03MNMP)].9(NMP).4(H20) 3.4, which has a rare (42.62)(4.62h topology; and the 20 networks [CU1.5(L3.4)(OMA)(H20h].3(CF3COO) 3.8 and [Ag(L3.5)].(BF4) 3.9 which have 63 topology. Coordination polymers 3.4 and 3.9 display 20-20 four-fold interpenetration. Organometallic coordination polymers and a discrete capsule were prepared with Ag(l) salts and tris-allyl-cyclotriguaiacylene L4.1 or hexa-allyl-cyclotriguaiacyclene L4.2, predominately through the formation of 1J2-vinyl interactions. The 3D networks [Agg(L4.1 h(H20h]·(L4.1 ).9(SbFs) 4.5 and [Ag2(L4.1 )z].2(SbFs) 4.6 display unusual topologies, or the discrete [Ag2L4.1z] capsule 4.7, were formed dependent upon stoichiometries of Ag(SbFs) and reaction conditions. Isostructural 10 networks [Ag2(L4.1 )(H20)z].2(X).2(MeN02) were formed when X = (BF 4-) 4.1 or (CI04-) 4.2. Formation of the 3D network [Ag2(L4.1 )(CF3S03)z] 4.3 or 20 network [Ag2(L4.1 )(CF3S03h] 4.3 was dependent upon Ag(CF3S03) stoichiometries. L4.2 formed the 10 network [Ag2(L4.2).(H20)].2(BF 4) 4.8 and 3D network [Ag4(L4.2)4(H20)4].4(SbFs).4(MeN02) 4.9.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available