Increasing Complexity in Adamantyl Thioethers Characterized by Rotational Spectroscopy.

We report on the synthesis and characterization using high-resolution rotational spectroscopy of three bulky thioethers that feature an adamantyl group connected to a sulfur atom. Detailed experimental and theoretical structures are provided and compared with the 1,1'-diadamantyl ether. In addition, we expand on previous findings concerning microsolvation of adamantyl derivatives by investigating the cluster formation between these thioethers and a water molecule. The investigation of such clusters provides valuable insights into the sulfur-centered hydrogen bonding in thioethers with increasing size and steric repulsion.