Is it possible to map the screenshot hotkey to a Wiimote button?

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Well, when you are completely out of options you can use some screen capturing software to create a video of you playing your games in Dolphin, and then use video editing software to gain pictures out of the video (your screenshots). Can be done with completely free software, but takes a lot more time. I can imagine though that you prefer this than having to press buttons while your are trying to play.