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For the Cake: Adjust oven rack to middle position and preheat oven to 350°F. Spray two 9-inch round cake pans with baking spray and line bottoms with parchment paper rounds. Spray once again with baking spray. Combine semisweet chocolate, cocoa powder, and espresso powder in medium bowl. Add boiling water and stir until chocolate chips are melted and mixture is thoroughly combined; set aside. Whisk together flour, baking powder, baking soda, and salt in medium bowl; set aside. Beat butter, sugar, and brown sugar on medium speed until light and fluffy, about 3 minutes. Add eggs, one at a time, beating well after each addition. Add vanilla and beat just to combine. Add chocolate mixture and beat to combine, about 1 minute, scraping down sides and bottom of bowl with rubber spatula as needed. Beat for 1 more minute to thoroughly combine. Add flour mixture in three batches, alternating with buttermilk. Divide batter equally between prepared pans and bake until tester inserted in center of cakes comes out clean, 25 to 30 minutes. Transfer cakes to cooling rack and cool in cakes pans for 10 minutes. Invert cakes directly onto cooling racks and cool completely, about 1 hour. For the Icing: Once cakes are cool, whisk the yolks, brown sugar, cocoa powder, and salt in large heavy-bottomed saucepan. Whisk in sweetened condensed milk, and 6 tablespoons butter and cook, whisking constantly over medium-high heat until mixture comes to a boil and thickens, 3 to 5 minutes. Stir in chocolate and cook until completely melted and incorporated. Off heat, stir in vanilla, and 1 cup coconut. Transfer mixture to bowl and cool slightly, about 10 minutes. To Assemble: Place one cake layer on cake stand or platter. With offset spatula or dinner knife, spread half of icing on cake layer, then, sprinkle with half of pecans. Top with second cake layer. Spread remaining icing on top of cake and sprinkle with remaining pecans and coconut. Serve.
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