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@absurdbird
If you're sealing between the glass and the frame silicone is fine. Double glazed units aren't supposed to be sealed with silicone but people do it all the time it could damage the seal between the 2 sheets of glass.
You can get high modulus (more movement) silicone specially for glazing but I generally use sanitary silicone (what you have)
I wouldn't use it to seal anywhere you intend to over paint. Nothing will stick to it.