From the start it's shown that these two are clearly seen by most of the school, as the most powerful couple in the school. Both of them seem to have power of the Eagles. It's shown that the two often agree with one another's decision and usually criticize people together, especially in the case of Alfie.
Early on it's shown that both share a very low opinion of Alfie as a whole, from the behaviour he's been displaying, often seen talking about Alfie meanly behind his back. However whereas Natalie seems to be more hot-headed and mean with her criticism, Daniel tends to be a lot more laid back and tends to take pity on people more, instead choosing to talk about people behind their backs instead.
Later on however, their relationship is strained when Daniel manages to accidently get a piece of shrapnel lodged in his leg. During his time in hospital, Natalie begins to make bridges with Alfie more and this causes ruptures when Daniel returns. Daniel is shown to be bitter about this, and questions Natalie on it. This bitterness drives Natalie away from him. Throughout the season, Daniel is shown to be unhappy about Natalie and Alfie's budding relationship, causing him to act nastily towards Alfie, an act in which Natalie doesn't agree with.
Later when Natalie comes back from a Tennis camp, she begins to act like her old self again, which causes Daniel suspicion, as he knows of her strong relationship with Alfie. During this time Daniel was uneasy around Natalie, not knowing what to do. Eventually, with the help of Ellali, it's revealed that Natalie has been hypnotised to act in this way and so he and Ellali try to de-hypnotize her, using a hypno-wheel. Eventually both work together as part of Team Galapagos, with Natalie pretending to still be hypnotised, in order to get close to Judy Goren, to allow her friends to switch out Judy's handbag with a bugged handbag.
During the second season of the show, the two had little to no interaction, as Natalie was still with Alfie early on and moved to the Ravens later, building a relationship with the Ravens Team captain; Iftach.