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Remember, only going back to post #25, before that it was a different person's system, yes if there is a motorised valve it is likely 230 volt AC, there were some 24 volts, but rather special, so unlikely using them. But all I see is a three core and earth cable, nothing to show what connected to.Existing setup appears to be zonal heating and existing thermostats are stating 230vac
We can consider the most likely, but 24 volt stuff does not like 230 volts AC, and likely no second chance, so we know brown and black go to 3 and 5, but we have no idea what the bare copper and grey wires are connected to, or which of the brown and black wires are feed or return.
I have not tested a Meross thermostat, so I have no idea what voltage supply is required to light up the display, since lit likely it is a 230 volt supply, I assume you are looking at the statement "I have got dual thermostats - does that make a difference? They were wired both the same" I also have duel thermostats, and they are wired the same, they are simply wired in parallel, they both control the same zone, it is simply the house varies in temperature due to sun on windows, so no one location can ensure the boiler fires when required.
It is too easy to assume, my light switch by front door a four gang switch, has three independent supplies to it, two from different RCBO's and one is from a smart relay and is extra low voltage, lumping all switches together from one supply would likely damage relay and would also trip the RCBO's.
So question has to be what test equipment is available. There is no point talking about loop impedance etc, if he has not got anything to measure it with.
The problem is one, is it 230 volts AC, and two is the grey a neutral wire, could also ask if the bare wire is earth, yes since 1966 earth wires must be run to installed equipment, but sometimes boilers are wired by plumbers who seem to think the regulations book is for holding a door open. Clearly not all, but I have seen some horrors wired by plumbers.

