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Lionel Messi became the first player to score in 16 consecutive Champions League seasons as he guided 10-man Barcelona to a 5-1 victory over Hungarian side Ferencvaros.
A late equaliser from Jannik Vestergaard earned Southampton a 3-3 draw away to Chelsea.
Germany scored once in either half to beat hosts Ukraine 2-1.
Olivier Giroud netted a double to take his international tally to 42 goals as the world champions crushed an injury and COVID-19-ravaged Ukraine 7-1 in a friendly.
Barcelona and Juventus were drawn together on Thursday in the Champions League group stage.
Spain scored a stoppage-time equaliser through Jose Luis Gaya to rescue a 1-1 draw away to Germany.
Goals from Marquinhos and Angel Di Maria put PSG 2-0 up at the interval and Juan Bernat added the third in the 56th minute for a comfortable 3-0 win over Leipzig.
Substitute Moussa Dembele struck twice as Olympique Lyonnais stunned Manchester City 3-1 to set up a semifinal clash with Bayern Munich.
With two minutes of normal time remaining, United States midfielder Tyler Adams snatched victory with a deflected shot from outside the box to set up a semifinal clash with Paris St Germain.
Paris St Germain scored two late goals, including a stoppage-time winner from substitute Eric Choupo-Moting, to beat outsiders Atalanta 2-1.