I have done so, and the paint promptly peeled. Made a mess.
For my glass overflow box, I used black silicone smeared in a thin layer so that it matched my black background. Use an old credit card or plastic putty knife.
+1, I made an acrylic oveflow box for a frag tank and painted it with Krylon Fusion, no problems with the paint in with a lot of sensitive corals. I used it for over a year and the paint looked still great a year later.
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