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If I have a smart TRV on every rad (bar one) then I don't need a main thermostat. If any TRV is calling for heat then turn the boiler on and provide some.
I don't know if this is how off the shelf stuff works but in theory I could build my own with some ZigBee TRVs, a WiFI relay and a Raspberry Pi.
I might do some extra detail like bedrooms are warm first thing in the morning on a school day to encourage teenagers out of bed but then cooler until they get home and go and do some homework (yeah right, just heat the telly watching room).
I'm sceptical about that approach. If you have a cold and draughty house like me then the time to heat a room is too long to usefully do something when someone starts using it. If you have a well insulated house then heating the room if someone is likely to use it isn't a big problem.
I basically want three modes: