Hello,
With STOP3 mode, since clocks remain active, I would presume that the SCI module remains functional. It would therefore seem probable that the first character would be received correctly. On the assumption that wakeup wold occur on the start bit transition, RDRF flag should become set about 170 microseconds later. The incoming character would then need to be read within the next 170 microseconds to avoid overrun.
I would assume that the SCI module must remain enabled for edge transition to work, so the peripheral clock must also be enabled continuously, with the associated current draw penality this requires.
To achieve lower current draw, perhaps using STOP2 mode, would require use of RTS/CTS hanshaking to provide wakeup. The originating end would first set RTS active, and would wait until CTS returned active, before sending the first character of a sequence. At the MCU end, the RTS signal might activate a KBI input, to cause wakeup. When the KBI interrupt is serviced after some wakeup delay, the return CTS line would be activated to allow transmission of the first and subsequent characters.
Another issue for either approach - the RS232 receive buffer for the received data (or RTS) will require to remain continuously active. This may mean that the interface device can never enter sleep mode, for reduced current.
Regards,
Mac