VMFS-5 datastore with sizes of up to ~64 TB are supported since vSphere 5.0. However, you may need to check whether LUNs/disks >2TB are supported with the controller you use. And yes - if it is supported - you can create the datastore using the vSphere Client.
Another thing, for vSAN, you need a minimum of 3 hosts with HDDs as well as SSDs!
André