there is a plug-in for Visual Studio that generates loadable code for that family of processors. I tried it, thought it was lame, expensive and don't think I ever got a debugger working. I would just use Eclipse with GCC as it is free an integrates well with GDB. C++ and C# are supported.
I wouldn't interface the CPU directly with external I/O. If you are switching, use a transistor, pretty simple and gives you an extra buffer for spikes coming from motors, etc. As someone mentioned, they might be 5v tolerant but still I have blown more of those boards by forgetting the 3.3v than I care to mention. Also, not all the pins are 5VT, just some, and I don't remember if the ADC pins are at all. All it takes is one mistake on a 3.3v pin and the chip is toast. The development boards are cheap though, I use the F4-discovery also another that has the TFT as well as Nucleo boards. The Nucleos I think are like $9 for a pack of them. I think I bought 10 from Newark.
Lastly, unless you have a lot of experience with embedded processors, I would start with something else. I have a ton of experience with this stuff and found the STMF4 family to be challenging. I start and stopped 3 times and went back to either PIC or Arduino for simple control systems. Lot of setup detail required for simple things. Once you get familiar with it, yes, it becomes easier and almost infinitely flexible but the learning curve is very high.
Lastly if you are looking at closed loop systems I would use external ADC chips/boards. Again, it is much easier and maybe cheaper to just replace the ADC compared to scrapping an embedded development board. I've been testing the 24bit LT products and they work great.