Molin's reign is notable because of Venice's participation in a prolonged war with the Ottoman Empire over Crete; this war was begun during the reign of Molin's predecessor Francesco Erizzo, and dragged on until 1669.
He was chosen as Procurator of San Marco on his merits; on the outbreak of the Cretan War (1645–1669), he was selected as Captain General of the fleet of the Republic of Venice.
[1] On 20 January 1646, after 23 ballots and considerable expense, Molin was elected as the 99th Doge of Venice.
During his first years as Doge, Molin strengthened Venetian forces in the area around Venice, and in Dalmatia, hoping to be able to carry the fight to Ottoman territory.
In an attempt to improve the situation, Venice led a fleet to the Dardanelles, where more Ottoman ships were destroyed, although a decisive Venetian victory still eluded Molin.