Andy Murray's return to Queen's fell flat as his 10-match winning streak on the British grass courts was ended by Australia's Alex de Minaur.
Former world number one Murray lost 6-3 6-1 and his hopes of earning a seeding for Wimbledon are all but over.
Spanish top seed Carlos Alcaraz earlier came through a tricky test to win on his debut at the Cinch Championships.
Alcaraz, 20, fought back against French lucky loser Arthur Rinderknech to win 4-6 7-5 7-6 (7-3) in the first round.
British number five Liam Broady, ranked 143rd, lost 1-6 6-4 6-3 to France's world number 46 Adrian Mannarino.
Broady looked on course for his best win by ranking of the season before the experienced Mannarino fought back.
In contrast to Alcaraz, Danish second seed Holger Rune had a smoother start to his grass-court season with a 7-6 (7-4) 7-6 (7-3) win over American world number 42 Maxime Cressy.
Rune, 20, will face British wildcard Ryan Peniston, who beat the Dane at Eastbourne last year, next.
I'll keep improving on grass, warns Alcaraz
Carlos Alcaraz is playing in his first grass-court tournament outside of WimbledonWhile Alcaraz has already won a Grand Slam title, topped the world rankings and been one of the dominant players on the ATP Tour this year, the Spaniard is still inexperienced on grass courts.
The US Open champion and recent French Open semi-finalist is playing only the third grass-court event of his senior career.
He had only ever played at Wimbledon in 2021 and 2022 before facing Rinderknech, who was a late replacement for the injured Arthur Fils.
Before his opening match at Queen's Alcaraz spoke about needing to improve his movement on the surface, but also believed his all-round game - aggression from the baseline, complemented by deft hand skills at the net - could lead to success in London this summer.
Initially Alcaraz struggled for fluency as Rinderknech's powerful serve and groundstrokes caused him issues.
But his movement improved as the match wore on, allowing him to show flashes of his undoubted shot-making ability.
"It was really difficult for me at the beginning to adapt my tennis and my game to the grass," said Alcaraz, who will play Jiri Lehecka in the second round after the Czech beat Spain's Alejandro Davidovich Fokina 7-6 (7-4) 6-3.
"It has been a good start for me. I feel really good but I will be better in the next round."