Part Number: TPS7A19
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Hi,
Thank you for asking us!
The PG pin cannot sink enough current to be useful as an active discharge. Even if the on resistance were low enough, the transistor just isn't designed to handle lots of current. The concern with using PG to drive an external active discharge is that the device would be trying to discharge itself during startup before the PG pin turns on, possibly hitting current limit or having inrush issues (depending on the load and discharge resistance). Using the EN signal is probably better to drive an external active discharge.
The simplest way is probably an external PFET connected to the EN pin.

Best,
Gregory Thompson