| Summary: | The synthesis of [3.3]dithia-bridged cyclophanes 7, 9 and 11 incorporating a fused heterocycle, thieno[2,3-b]thiophene is described. The structures are established by 1H NMR analysis and, in the case of 11, also by single crystal X-ray crystallography. Conformational analysis by variable temperature NMR suggests that cyclophanes 7, 9 and 11 exhibit conformationally rigid bridges and rings at least up to 130 °C. Energy minimization of 11 revealed anti-11 to be the most stable conformation. Although, the computed energy difference between the most stable conformation anti-11 and the next higher energy conformation syn-anti-11 is only 2.98 kJ/mol, it is intriguing that 11 does not exhibit thia-bridge inversion even at elevated temperatures.
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