Germany and Italy on Friday locked up places in the Davis Cup last eight, while Britain and France were eliminated and US Open champion Carlos Alcaraz made a losing return to the court.
In Bologna, Matteo Berrettini crushed Argentine Sebastian Baez 6-2, 6-3 in 71 minutes and then Jannik Sinner beat Francisco Cerundolo 7-5, 1-6, 6-3 to give Italy a winning 2-0 lead in the tie and ensure they would in the top two places in Group A.
Italian pair Simone Bolelli and Fabio Fognini then lost the doubles to Maximo Gonzalez and Horacio Zeballos in three sets.
In Hamburg, Kevin Kraweitz and Tim Puetz gave the hosts a 2-1 victory when they beat Belgian pair Sander Gille and Joran Vliegen 4-6, 6-2, 7-6 (7/5) in the deciding doubles.
"Nights like this live long in the memory," said Germany captain Michael Kohlmann.
Jan-Lennard Struff had given Germany a winning start by beating Zizou Bergs 6-4 7-6 (11-9) but David Goffin fought back from a set down to overcome Oscar Otte 3-6, 7-6 (9-7), 6-3.
Germany's victory eliminated France which had lost its opening two ties in Group C.
Playing in his home city of Glasgow and in his 50th Davis Cup rubber, Andy Murray could not conjure any magic as he and Joe Salisbury lost a tight doubles decider to Wesley Koolhof and Matwe Middelkoop
The Dutch pair won 7-6 (7/0), 6-7 (6/8), 6-3 to join the United States with two victories in two ties in Group D.
Dan Evans had given the hosts the lead by beating Tallon Griekspoor 6-4, 6-4.
Botic Van De Zandschulp responded by crushing world number eight Cameron Norrie 6-4, 6-2.
In Valencia, Carlos Alcaraz, the youngest ever men's world number one at 19 after his US Open triumph, had a bittersweet homecoming as he lost to Felix Auger-Aliassime 6-7 (3/7), 6-4, 6-2 in his country's Group B loss to Canada.
Given an ovation by the home fans after his first Grand Slam conquest on Sunday, the Spaniard and his Canadian opponent played out a thrilling second singles rubber, with Canada levelling the tie at 1-1.
Alcaraz, from nearby Murcia, had watched from the sidelines on Wednesday as Spain beat Serbia 3-0.
On Friday, after the players had split two fiercely-fought sets, Alcaraz faded, perhaps unsurprisingly after his marathon matches in New York.
World number 13 Auger-Aliassime broke straight away and then again to go 4-1 ahead, holding off the Spaniard despite strong encouragement from the crowd.
Roberto Bautista had put Spain 1-0 up in the tie after coming from behind to beat Vasek Pospisil 3-6, 6-3, 6-3.
Pospisil and Auger-Aliassime rallied for a 4-6, 6-4, 7-5 doubles win over Marcel Granollers-Pujol and Pedro Martinez Portero to move Canada to the top of the group and within sight of advancing.