Using an indexed database, if you make a new rich text document on DTPO, you have to use the contextual menu “Move To External Folder” for it to move into the Finder.
While that’s OK as far as it goes, there should be a new command/toolbar button which will make new rich text which immediately goes to the external folder.
Or would that cause untold chaos and confusion?
Maybe “could be”… 
Here is a simple, simple script that does just that: It moves files to the externally indexed folder (and it’s got a custom goofy little icon too 
)
Quit DEVONthink, decompress the ZIP and put the Applescript in ~/Library/Application Support/DEVONthink Pro 2/Scripts/Toolbar.
After you relaunch DEVONthink, right-click the Toolbar and choose “Customize Toolbar…”. You should find the script toward the bottom. Drag it where you want it in the Toolbar, and done.
DT_Deconsolidate.scpt.zip (1.55 MB)
I might increase the icon goofiness at some point, but many thanks !
My pleasure. And hopefully, it inspires you to explore more ways YOU can customize DEVONthink in ways most apps don’t allow. 
Cheers!