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Preheat the oven to 425°F (220°C). Generously butter four cups of a standard 6-cup muffin tin (or four 6-oz ramekins), then dust each with cocoa powder, tapping out any excess, so the cakes release cleanly.
Combine the chopped chocolate and 6 tbsp butter in a heatproof bowl set over a saucepan of barely simmering water, making sure the bowl does not touch the water. Stir occasionally until both are fully melted and the mixture is smooth, about 3–4 minutes. Remove from heat and let cool for 2 minutes.
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