Looks like there's an assembler for programming the PIO peripheral; they seem quite capable with two IO registers and two scratch registers.

I've used a similar sort of embedded state machine inside EFM8 microcontrollers before. They're great not just for implementing custom communication protocols, but also for offloading simple tasks: one example I've coded before is that you can offload software key debouncing to the state machine, and even get an interrupt on keypress. This greatly simplifies the main loop as you don't need to dedicate polling time or write debounce calculations!