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The NL threatened again in the third, loading the bases against Yankees reliever Dellin Betances, getting two walks and a single.
But Betances got Murphy to bounce out to end the inning.
Molina, 34, became the oldest catcher to homer in an All-Star Game, beating the previous record held by Yogi Berra.
"I felt like a little kid running the bases," Molina said.
Both closers stranded runners on third in the ninth.
The Los Angeles Dodgers' Kenley Jansen struck out three of the four batters he faced, and his AL counterpart, Craig Kimbrel of the Boston Red Sox, punched out two batters, including the New York Mets' Michael Conforto to send the game to extra innings. Andrew Miller pitched a scoreless bottom of the 10th for the save, getting help on a diving catch in right field by the Detroit Tigers' Justin Upton.
Bryce Harper, the Washington Nationals star, endeared himself to fans in Miami with his choice of cleats.
Read More Projected stats for the rest of the season as calculated by Steamer, which uses past performance and aging trends to develop a future projection for players.
The first NL reliever, Pat Neshek of the Philadelphia Phillies, pitched a scoreless second inning, thanks to his defense.