There is a type of adjective "タリ活用形容動詞" in classical Japanese, e.g., 堂々たり, 悠々たり or 平然たり. The adverbial form of these adjectives is "the stem + と".
e.g.
堂々と振舞う
悠々と逃げる
平然としている
It's equivalent to に in the adverbial form of ナリ活用形容動詞, which is the classical form of na-adjectives.
e.g.
哀れなり(= 哀れだ in modern Japanese) --> 哀れに思う
優雅なり(= 優雅だ) --> 優雅に舞う
見事なり(= 見事だ) --> 見事に作る
Speaking strictly, 辟易 is a -suru verb, so the adverbial form should be 辟易して, but 辟易とする is also used customarily. Thus, 辟易と functions as an adverb there. 辟易(と)してため息をついている makes more sense, maybe?