Synthesis and complexation properties of naphthalene ring-based receptors

Tran, Huu-Anh (2006) Synthesis and complexation properties of naphthalene ring-based receptors. Doctoral (PhD) thesis, Memorial University of Newfoundland.

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Abstract

The work described in this thesis deals mainly with the synthesis of new molecular receptors containing naphthalene-ring units ("calixnaphthalenes"), and their solution complexation properties with neutral guests such as fullerene (C60 and C70 ) and/or cationic guests, e.g. tetramethylammonium chloride and/or several metal ions (alkali metal and silver ions). -- In order to develop practical methodology for the solution complexation studies using 1 H NMR spectroscopy, thiocorannulene derivatives synthesized by the L.T. Scott group were employed as model hosts with fullerenes (C60 and C70 ) in CS2 . The results of this work are described in Chapter 2. The study revealed that pentakis(1,4-benzodithiino)corannulene (53 ) formed the strongest 1:1 complexes of any corannulene derivative with C60 and C70 reported to date. -- In Chapter 3, the syntheses of calix[4]naphthalenes and the attempted modification of the narrow-rim of tert -butylcalix[4]naphthalene 18 via alkylation, or via the Sonogashira coupling reaction are reported. In addition, a recent reinvestigation of the complexation properties of calix[4]naphthalenes such as 17 and 18 with C60 and C 70 in toluene (toluene-d8 ) and CS2 was conducted using 1 H NMR and/or UV-vis absorption spectroscopy. Under the conditions studied, only 18 was revealed to be a good host for C60 and also for C70 in toluene- d8. -- In Chapter 4 the syntheses of ethoxycarbonylmethoxy ethers ("hexaester" 123 and "octaester" 124 ) of homocalix[n ]naphthalenes are described. These new compounds were employed as alkali ionic receptors using a two-phase extraction (CHCl3 -H2 O) system and compound 123 was shown to be a highly selective receptor for potassium ion under the conditions studied. -- The work described in the remaining Chapters concerns the synthesis and/or complexation properties of the homohetero-bridged calixnaphthalenes, including homooaxa-159a-d , 160a and 160d , homothia- 205-208 , and homoaza analogues 264a-d . While octahomotetraoxacalix[4]naphthalenes 159a and 159b were shown to be good hosts for TMACl in CDCl3 with 1:1 binding ratio, no complexes were observed to be formed between these new homothia receptors with TMACl. In contrast, the transition-metal ion Ag+ , formed 1:1 host-guest complexes with octahomotetrathiaisocalix[4]naphthalenes 205a and 205b .

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