BobT So be warned, what you see in the Octopus app can be - initiallly, misleading. Happy for @MrMessy to chime in here.
My experience is as follows. You are allocated a PEAK charging slot by Octopus to charge your car when they want to. WW picks up this allocated slot and this will then set your home load to use the cheap rate also. The slots are in 30-minute increments, so even if your car finishes charging mid-slot, you are allocated the full 30-minute slot at the low OFF-PEAK rate. Now here comes the kicker, which is what I believe you are trying to illustrate above. Octopus shows that you have used electricity during the PEAK window at the full PEAK rate. Counterintuitive from the Octopus app, me says! At some point later - it can be 24/48/72 or even more hours later, your app view will update, and it will show you in that 30-minute slot that you actually have been charge at the OFF-PEAK rate.
Therefore, you need to do nothing in the Octopus app. In fact, if you try to interfere, you will probably get one or more of the items in a flat spin.
WW will 99.99% of the time control the battery and put it back into Eco mode so that the house load runs from your now fully charged [fingers crossed] battery.
The best way to confirm what I have put above, is, on your next Bill from Octopus, there will be a day-by-day breakdown of each 30-Minute period and what you have actually been charged - I provide an example below for reference on a day in January when Octopus provided me some during the day charging slots.
Hopefully, this clarifies your question.

Any comments on this assertion are welcome from anyone who is on the IOG tariff.