Except that you said that the tank stat turns off the boiler and pump once it is satisfied. If that is true, the zone valve can open as much as it likes but the radiators won't get hot if the boiler and pump have been turned off.
But assuming that they *do* get hot by some mechanisn as yet unexplained, there is nothing to stop the DHW from overheating when the CH is on because water will still circulate round the HW circuit regardless of the tank stat.
In days of yore, when systems were common which had gravity HW and pumped CH, programmers had an optional link which forced the boiler on when there was a CH demand - but they probably don't do that now because there must be very few gravity HW systems left.
I don't see a problem with that. I have a similar situation - with an outside light which is controlled by a PIR. I have also wired a by-pass switch which sends power direct to the light so that I can keep it on. The PIR doesn't seem to object to that. [As far as I am aware, the PIR switches the mains directly rather than by means of a relay].