Abstract. The syntactic complexity of a regular language is the size of its syntactic semigroup. This semigroup is isomorphic to the transition semigroup of a minimal deterministic finite automaton accepting the language, that is, to the semigroup generated by transformations induced by non-empty words on the set of states of the automaton. In this paper we search for the largest syntactic semigroup of a star-free language having n left quotients; equivalently, we look for the largest transition semigroup of an aperiodic finite automaton with n states. We introduce two new aperiodic transition semigroups. The first is generated by transformations that change only one state; we call such transformations and resulting semigroups unitary. In particular, we study complete unitary semigroups which have a special structure, and we show that each maximal unitary semigroup is complete. For n 4 there exists a complete unitary semigroup that is larger than any aperiodic semigroup known to date. We then present even larger aperiodic semigroups, generated by transformations that map a non-empty subset of states to a single state; we call such transformations and semigroups semiconstant. In particular, we examine semiconstant tree semigroups which have a structure based on full binary trees. The semiconstant tree semigroups are at present the best candidates for largest aperiodic semigroups. We also prove that 2 n − 1 is an upper bound on the state complexity of reversal of star-free languages, and resolve an open problem about a special case of state complexity of concatenation of star-free languages.