We search for the largest syntactic semigroups of star-free languages having n left quotients; equivalently, we look for the largest transition semigroups of aperiodic finite automata with n states. We first introduce unitary semigroups generated by transformations that change only one state. In particular, we study unitary-complete semigroups which have a special structure, and show that each maximal unitary semigroup is unitary-complete. For [Formula: see text] we exhibit a unitary-complete 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. 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.