Note that Unix came first (the wording of your question makes it look like it was the other way round).
DOS inherited the dir
command from CP/M, which got it from VMS. The /
character to introduce options (which forced DOS to adopt a different character as the directory separator, when directories were introduced) had the same origin.
Why didn't the VMS designers follow Unix? Because when VMS was designed, Unix was still young, and hadn't become the de facto standard that it would later become (in part thanks to the POSIX standardization effort). VMS and Unix had different designs in many respects; I doubt there was a deliberate effort to make them incompatible. CP/M and DOS, and early versions of Windows followed VMS because there was no compelling reason to pick Unix over VMS at that time; the lead designer of Windows NT had previously worked on VMS, which further influenced Windows towards VMS rather than Unix. Later, when Unix came out as the standard operating system on servers, Windows was too firmly entrenched as different to change. Nonetheless, Windows did acquire some limited amount of POSIX compatibility (sometimes through third-party software); for example internal APIs do accept /
as a path separator.