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Porto, winners in 2003 and 2011, last met Serie A club Roma in a Champions League last 16 clash in 2019, in which the Portuguese side emerged victorious.
Turkey’s Fenerbahce face Belgium’s Anderlecht, while fellow Super Lig club Galatasaray take on AZ Alkmaar.
Ajax Amsterdam, champions in 1992, will meet Union SG and FC Twente play Bodo/Glimt of Norway.
The top eight sides automatically qualified for the last 16 while the teams that finished ninth to 24th will compete in the two-legged playoffs.
Premier League sides Manchester United and Tottenham Hotspur, among the favourites to win the tournament, secured automatic qualification to the Europa League last 16.
United and Spurs could face the winners of the tie between Midtjylland and Real Sociedad, or the winners of AZ Alkmaar v Galatasaray.
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