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Barcelona stepped onto the pitch at Estadi Olimpic Lluis Companys with a 3-2 advantage from their previous clash in Paris.
Raphinha's goal, courtesy of Lamine Yamal's skillful play, fueled their hopes of securing a spot in the semi-finals.
However, the game took a dramatic turn in the 29th minute when Ronald Araujo received a red card for a foul on Bradley Barcola.
PSG seized the opportunity, applying relentless pressure on Barcelona's defense. A mistake from Joao Cancelo paved the way for Ousmane Dembele's goal, followed by Cancelo fouling Dembele in the box, granting Kylian Mbappe the chance to complete the comeback.
Xavi had dreamed of concluding his Barcelona tenure with a triumph at Wembley, following a 13-game unbeaten streak since announcing his departure in January.
Yet, his hopes of a fairytale ending were dashed when he was ejected for kicking water bottles on the sidelines.
Despite constant jeers from the home crowd, Dembele showcased a performance befitting his status as Barcelona's second most expensive signing at £135 million in 2017.
Initially regarded as Mbappe's successor upon his move to PSG last year, the 26-year-old is now demonstrating the attacking prowess worthy of comparison to the player who, with 48 goals, has equaled Zlatan Ibrahimovic as the 10th highest scorer in Champions League history.