It sounds like you've already got your environment set up if you're able to debug the application, so that's the first thing I was going to suggest in a knowledge-transfer situation. Some general things that I would get from the developers before they depart:
A list of third-party components that the application uses, along with license information and website logins if applicable.
Access to every part of the environment that this thing runs on, both production and development. That means the source code management system, database server(s), etc. It sounds like you have some of these already but make sure you get access to absolutely everything.
If your development environment was given to you "as is" (i.e. you took it over from one of the departing developers, make sure you know how to rebuild it from scratch. They might have a document that describes the process of building a development box, but if not maybe you can get them to show you how to set up a fresh machine.
Three will go a long way towards this, but if setting up a server to run the application is different in any way from setting up a development environment, you'd want to know how so you can diagnose server configuration issues if they crop up, or even rebuild a server. Although this sort of thing may be someone else's responsibility depending on your organization.
Once you have those, you probably want to get some understanding of why the application does the things that it does. That will give you the context you need to understand support and enhancement requests when they come in.
Are the original developers the only source of this information, or are there business people who you will be working with after the developers leave? One of the first things I try to do when starting on an existing application that's new to me is to find someone who knows the business well and have them give me a high-level run-down of the application's purpose in life. From there you can go into more detail on individual components/features/whatever as needed. The business people may be a better source for this information than the developers are, so you may want to try them first.
Hopefully some of that helps.