The 100m² maximum floor area is just a rule of thumb to reduce the risk of too many appliances being connected to any one circuit and causing one leg to be overloaded for long periods of time. Further factors to consider when deciding on the floor area covered and the length of cable used is voltage drop and R1+R2 and subsequently ensuring your Zs reading is within the limits set by BS7671.
As it is a rule of thumb, if you can ensure that VD and Zs are still acceptable, then there is nothing stopping you going over the 100m² limit, although splitting it into 2x 4mm² radials would be better than wiring it as a ring final circuit.
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