Boil water. Transfer 3/4 cup of boiling water to bowl. Stir in cocoa until dissolved to form chocolate mixture and set aside.
With a wire whisk, mix flour, baking soda, cinnamon, salt and chipotle powder in a separate bowl and set aside.
In a large mixing bowl, mix sugar, butter and eggs until light and fluffy. Add buttermilk and vanilla and mix well.
Add flour mixture to the wet ingredients in three additions, alternating with chocolate mixture in two additions, ending with flour mixture. Beat until combined with each addition.
Add pureed chipotles and beat until combined.
Scoop batter into prepared cupcake trays. Bake for 13-15 minutes and cool completely.
Ganache: Combine chocolates and heavy cream in medium bowl. Microwave on high in 30 sec intervals. Stir in between. Gradually add sugar and whisk mixture until smooth. Let cool. Pour into squeeze bottle.
Assembly: Remove paper liners. Cut cupcake in half horizontally. Place a small scoop of ice cream in between the two cupcake halves. Top with another scoop of ice cream and drizzle with Chili Chocolate Ganache. Sprinkle chopped chocolate shavings to top it off. Enjoy right away.
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