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Rublev, 23, had previously won tournaments in Doha, Adelaide, Hamburg and St Petersburg and improved to a Tour-leading 39 wins in 2020 -- tied with world No. 1 Djokovic.
Both Djokovic and Thiem were beaten in straight sets by Lorenzo Sonego and Andrey Rublev respectively in the quarterfinals.
Djokovic, who won the Australian Open in February for his 17th major title, is still No. 1, with Nadal at No. 2, followed by US Open champion Dominic Thiem and Federer.
Greek fifth seed Stefanos Tsitsipas reached his second Grand Slam semifinal as he raised his game after a slow start to defeat Russian Andrey Rublev 7-5, 6-2, 6-3.
Thiem put in a sublime performance to dismantle Australian Alex de Minaur's challenge, while Medvedev continued his march towards a first Grand Slam title with a clinical victory over childhood friend Andrey Rublev.
Russia were initially declared winners after two Indian players - Nihal Sarin and Divya Deshmukh - lost out on time in the final after suffering a disconnection with the server.
Dimitrov was one of the players who took part in the Adria Tour with the likes Novak Djokovic, Alexander Zverev and Dominic Thiem among others.
Shapovalov and Pospisil, who have shouldered the burden through four ties in La Caja Magica this week, combined to beat Andrey Rublev and Karen Khachanov 6-3 3-6 7-6(5).
The world number one almost single-handedly hauled his country home and set up a final with Canada in the inaugural edition of the revamped competition on Sunday.