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I don't know whether this has anything to do with your problem, but I recall that a couple years ago when I switched from Calibre 1.x to 2.x, it crashed when switching libraries. In my case, it had something to do with the Open With plugin. Installing a previous version of the plugin fixed the problem.
If you have the Open With plugin installed, you might try temporarily disabling it to see if that's causing the issue. If not, you could try disabling other plugins as well.
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