Australians Milos Degenek and James Holland have starred as their European sides booked a place in the Champions League play-offs while the giants fell in the third round of qualifying, with Porto and Celtic headlining a day of casualties.
Socceroo defender Degenek played the full 90 minutes for Red Star Belgrade who sensationally prevailed 7-6 in a dramatic shoot-out over Copenhagen.
After a solid game in defence, Degenek was one of the players who then managed to convert from the spot as a whopping 22 penalties were taken to secure the victory.
Penalties were required after the Copenhagen-Red Star tie ended 2-2 on aggregate following Tuesday's 1-1 stalemate at Telia Parken. Red Star will now meet Young Boys for a spot in the Champions League group stage.
Fringe Socceroo Holland's Austrian side LASK Linz defeated FC Basel 3-1 thanks to goals from Reinhold Ranftl, Thomas Goiginger and Marko Raguz.
Holland starred, helping set up the first goal and providing the assist for the second as they secured their place in the play-offs where they will meet Club Brugge.
The news was not so good for fellow Australian Aziz Behich's side Basaksehir who were knocked out by Olympiacos.
Tom Rogic and Daniel Arzani's Celtic also crashed out along with FC Porto following respective losses to Krasnodar and CFR Cluj.
Meanwhile last season's semi-finalists Ajax managed to advance to the play-off round in what was a day of upsets.
Porto – who had featured in the Champions League group stage in each of the last three campaigns, including a run to last season's quarter-finals – were upstaged 3-2 by visiting Krasnodar on Tuesday.
Krasnodar blitzed Porto with a three-goal first half thanks to Magomed Suleymanov's brace as the Russian side prevailed on away goals after a 3-3 draw.
Scottish champions Celtic were denied a play-off berth by Cluj, whose 4-3 victory on the night in Glasgow secured a shock 5-4 success across two legs.
Celtic led the second leg 3-2 after 76 minutes but Billel Omrani and George Tucudean struck inside the final 10 minutes to silence Parkhead and give the Romanian outfit a memorable victory.
Captain Dusan Tadic was at the double as Erik ten Hag's Ajax held on to beat PAOK 3-2 in Amsterdam, where the Eredivisie holders escaped 5-4 on aggregate.
Tadic scored twice and missed a penalty as Ajax's hopes of repeating last season's remarkable Champions League run stayed alive amid uncertainty over the future of Real Madrid target Donny van de Beek.
Elsewhere, Dynamo Kiev bowed out as Club Brugge, Dinamo Zagreb, APOEL and Rosenborg progressed.
Champions League play-off ties:
CFR Cluj v Slavia Prague
APOEL v Ajax
LASK v Club Brugge
Dinamo Zagreb v Rosenborg
Young Boys v Red Star Belgrade
Olympiacos v Krasnodar