Line a 10" square baking pan with plastic wrap, being sure to cover all of the inside of the pan.
Divide the water equally into two bowls, and set one of them aside. In the other bowl, sprinkle the powdered gelatin and salt over the top of the water. Do not mix, let it sit and bloom while you prepare the other ingredients.
In separate bowl, mix together the hot water, cocoa powder, vanilla, and espresso powder into a chocolatey paste. Set aside.
Pour the reserved bowl of water into a saucepan along with the sugar and corn syrup and mix together. Put the pan over medium heat until it reaches a temperature of 250°F / 121°C. Do not stir the mixture while it heats - it will boil and the sugar will dissolve into a clear syrup.
While you are waiting for the sugar syrup to come to temperature, get your stand mixer ready with whisk attachment. Put the bloomed gelatin into the bowl of the mixer.
As soon as the sugar syrup reaches 250°F / 121°C, remove it from the heat right away. Turn the mixer on medium and let it break up the gelatin for a few seconds, then start pouring the sugar syrup into the bowl in a slow, steady stream. Try not to drizzle the syrup down the side of the bowl or hit the whisk, just aim for the space in between and lead it flow in gradually.
Once all the sugar syrup is added, add the chocolate paste mixture, then turn the mixer up to high speed and whip for 10 minutes.
Towards the end of the 10 minutes, melt the chocolate in the microwave in 30 second increments until completely melted. Set aside until needed.
After 10 minutes, the marshmallow mixture should be thick and glossy, and should be forming shapes as you whisk it, like meringue or whipped cream would do. If it's not thick enough, keep beating on high speed until it thickens. When it's done, feel the side of the bowl - it should have cooled significantly, but still be very slightly warm to the touch.
Once the marshmallow is ready, remove the bowl from the mixer and pour in the melted chocolate, swirl it into the marshmallow a little, but not so much that it incorporates - a few turns with a spatula should do the trick. Make sure you work quickly at this point as the longer you wait to pour the marshmallow the harder it will be to get out of the bowl!
Pour the chocolate marshmallow into the prepared cake pan and use a spatula to spread it out to the corners. It can make it easier if you coat your spatula with a little flavorless oil beforehand to help you get it out of the bowl without too much sticking.
Mix together the powdered sugar and remaining cocoa powder in a bowl until thoroughly combined. Sprinkle some of the mixture generously over the top of the marshmallow so it is completely covered.
Leave the marshmallow out at room temperature overnight to set (or at least for 8 hours). Do not cover it with plastic wrap as we want it to dry out a little.
Once the marshmallow has set, flip the cake pan upside down to turn it out onto your work surface. Remove the plastic wrap and then dust all the exposed marshmallow with more of the powdered sugar/cocoa powder mix. Let it sit to dry out like this for a further 2-3 hours.
Coat a sharp knife with flavorless oil and some of the powder mixture, then cut the very edges off the marshmallow to get nice straight edges. Slice the marshmallows into whatever sized squares you like.
Notes
If you don't have a 10" square cake pan, you could also do this in an 8" or 9" pan, the marshmallows will just be thicker. Or you could use a rectangular pan. While normal marshmallows would be heated to 240°F, also known as the softball stage, these chocolate marshmallows require a slightly higher temperature so they can accommodate the liquid in the chocolate paste we will add to it. Try to use dutch processed cocoa powder if you can, it gives a much better flavor and texture in baking than other cocoa powders.