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check out www.infragistics.com.
they have a huge library for controls such as xp/office 2003 like menus/toolbars/buttons/tabbed interfaces .... and the list goes on. you can download and eval for 14 days of usage. Price is not that bad, around 500$.
I tried using the eval, and was able to get an impressive office 2003 like app in a few days.
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Non-rectangular windows are cool,fun, and not very difficult with GDI+. Do some research on the GraphicsPath Class. With an instance of this class, you can create all sorts of custom shapes, then assign this instance of GraphicsPath to the "Region" property of your form. You'll have sleek looking forms in no time! have fun!
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You can buy some nice looking controls from sharplibarary
http://www.sharplibrary.com