Appication main window gets set to the window which is the start up window for an application. So, in your case it will be Login window and since you have closed it, Application.Current.MainWindow
will return null.
In case you want to get MainWindow, you can get it from Windows collection
like this:
MainWindow mainWindow = Application.Current.Windows.OfType<MainWindow>().First();
mainWindow.contentControl.Content = new UserControlNEWControl();
To use OfType<T>() and First()
extension methods, add System.Linq
namespace in your class.