The ECU is a computer that has multiple sensors (stating the obvious, I know

) to 'keep an eye' on what's happening within the engine and other systems, it reacts instantly to any changes. A change in fuel should be recognized pretty much immediately by an ECU as the increased octane level will change what is happening within the combustion chamber which is something the ECU will react to within milliseconds .... not sure where the idea of the need of running the car in on a full tank came from but it seems to be a common one?
Most of the point of higher octane fuels is also to reduce the tendency of similar density fuels to detonate (knock) under compression due to higher activation energy requirements and therefore makes them more efficient and better for the engine. This becomes important at full throttle where the manifold pressure can be equal to or > atmospheric pressure (in the case of turbo charged engines). In my view the less likely the fuel is to 'knock' then the more efficient it will be, particularly at full throttle, giving an increase in power produced and smoother power curve.
A common misconception seems to be that higher octane fuels increase the hydrocarbon or oxygen availability and therefore produces an increase in power and fuel efficiency, which is not the case as a higher octane fuel have no direct effect on hydrocarbon or oxygen availability.
The effect will be on the air/fuel ration with higher octane fuels being more efficient and therefore not needig to be as high in the ration mix, using less fuel

I know I commonly achieve 5-8mpg more on higher octane fuels.... but then I do like to open the throttle
Without meaning to be offensive, the idea that there is only a placebo affect in using higher octane fuels in performance engines is ridiculous and disproven in many tests, even those done by 'car mags'.
I have not researched to find out the reasons that might be behind why I find Tesco Momentum 99 RON fuel not as smooth and certainly not as efficient as BP/Shell 97 RON fuel.... maybe it was a bad batch that I used in the cupra, only tried it once. I know have preferred T99 in previous cars .... maybe i'll give it another go?