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The Gunners have lost their opening three league games of a season for the first time since 1954-55.
The substitute scored an extra-time winner as Brazil edged Spain 2-1.
Mikel Oyarzabal struck the winning penalty after Switzerland's Ruben Vargas fired over the bar as Spain won 3-1 in a shootout following a 1-1 draw.
Alvaro Morata and Mikel Oyarzabal's strikes in extra time made the difference.
Croatia exited from Euro 2020 in a 5-3 extra time defeat by Spain after a riveting fightback in their last 16 clash.
Messi scored twice as Barcelona thrashed Athletic Bilbao 4-0 in the Copa del Rey final on Saturday to win the trophy for a record-extending 31st time with all the goals coming in the last half an hour.
Pierre-Emerick Aubameyang's 87th-minute header secured Arsenal a 3-2 win over Benfica for a 4-3 aggregate victory after the Premier League side had been staring at the exit door.
United became only the second team to win a Premier League game 9-0, matching their 9-0 win over Ipswich Town in 1995 and also Leicester City's away rout of Southampton in 2019.
Manchester United were held to a 2-2 draw at Leicester City while Manchester City climbed to fifth thanks to a 2-0 win over Newcastle United.
Manchester City got back to winning ways with a 1-0 victory at in-form Southampton while Newcastle United were held to a 1-1 draw at home to struggling Fulham.