The synthesis and full characterization of a series of chiral [Zn(salen)] [salen = N,N′-bis(salicylidene)ethylenediamine dianion] complexes comprising a 1,2-diphenylethane backbone is reported. The preparation method reported here simplifies the previously communicated methodology for these types of Zn complexes that utilized air-sensitive ZnEt₂ (or similar) as the metalating reagent. X-ray molecular structures are also reported for representative examples of this family of [Zn(salen)] complexes. A wide range of functionality is shown to be accessible by means of the present route, thereby amplifying the potential use of these (Lewis acidic) Zn complexes as molecular building blocks. Examples in this work include the formation of supramolecular assemblies having built-in bifunctionality using versatile Zn–N and Zn–O coordination motifs as guiding tools.