Unity uses Mono in order to achieve multi-platform compatibility. Because of that it wouldn\'t make sense to use .NET 4.0 or higher, since Mono does not support them either
According to this site it has to do with the support of other computers. Most computers will be able to run .NET 2.0 but not 3.5. It also runs C# 4, I believe, 5, but definitely not C# 6. For some reason, they're kind of behind on things. I think its because there's little benefit of doing upgrading everything.