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If you are talking about the Library panel and After Effects then that is not working as of the latest build. You'll have to use another application to sample the color and add it to the color themes panel. It is on the list but for now the easiest way to create a theme is to save a frame as a PSD or other image file and import it to an Illustrator document (easiest and most versatile color theme generator I have used recently) or open in Photoshop and use the Color Theme panel then save it to your library.
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I have a color from a video that I'd like to sample, using an eyedropper or whatever, to add to one of the swatches in my theme, but I can't figure out how to do this. It seems like it a basic feature of a color panel, but I'm somehow missing it.
because you can't. you can only create new colors from the extension and sample from it to Ae and not backwards... sucks right? you can always type them numerically though in the extension.... if you if need RGB 8-bit numbers just change the info panel options to 8bit.
Thanks guys. Things in AE are usually so fully-featured that I never considered the fact that one couldn't just do it. I guess this is one panel that still has room for growth.
If you want swatches you might want to take a look on "ray dynamic color" script. Uou can easily create a color pallate that is accesible through a panel.