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Cristiano Ronaldo’s extra-time miss from the spot took the match into a shootout.
Spain, bidding for a record fourth Euros title, will play a third-placed team in the last 16 in Cologne on June 30
Hungary must wait to see whether they will qualify for the last 16 in one of the places reserved for the best four third-placed finishers.
The Germans will find out their last 16 opponents on Tuesday.
All outcomes are now available on the final night on Wednesday when Belgium play Ukraine and Slovakia play Romania.
Guler became the youngest player to score on his debut at a Euros aged 19 years and 114 days - beating Cristiano Ronaldo's record.
Portugal predictably dominated the ball, with 70% possession, 19 shots and 13 corners.
Dortmund: Italy recovered from the shock of conceding the fastest goal ever scored at a European Championship to beat Albania 2-1 on Saturday as Alessandro Bastoni and Nicolo Barella ensured the defending champions made a winning start to the tournament. Tens of thousands of raucous, red-shirted
Ukraine can still book a spot at a fourth consecutive European Championship via the playoffs in March.
Defeat for Italy, who led through Gianluca Scamacca before England overtook them with two goals from their all-time record scorer Harry Kane – the first a penalty -- and one from Marcus Rashford, leaves the Europen champions in a precarious third place.