Where is "Save as PDF to DevonThink..." print workflow?

You need to set Preferences > Import > Destination to Select group.

From help Help > Documentation > Preferences > Import:

DESTINATION

Choose the default destination where incoming data is stored.

  • Select group: A group selector is shown that lets you choose the destination. The group selector appears as a black panel floating on top of all other windows. Use it to select the group where you want to file the items.

  • Global inbox: The data is stored in the global inbox.


PS It’s a good idea to look at DEVONthink 3 as a completely new app which means you should read the help.

You could use this script to index a duplicate of DEVONthink’s help. Searching an app’s help content from inside DEVONthink is far easier than searching inside the macOS help viewer (at least for me).