Also in terms of a general consumer app vs. a team-based app, perhaps the terminology can reflect this? Instead of a contact being a "buddy" (which doesn't sound professional) what about just calling them "Contacts" and the ones you want to be able to insta-chat with you can be marked as Trusted?
With respect to biot's comment, a lot of teams have found effective ways to work remotely, but a lot of teams are still looking for more fluid communication channels. QuicklyChat isn't going to appeal to everyone, especially not at first, but it definitely seems like we've struck a chord with a fair number of people.
http://en.wikipedia.org/wiki/Mike_(cellular_network)
That technology definitely struck a chord with a niche audience. I think the product's name of MiKE was chosen to appeal to male-dominated industries such as construction where it essentially functioned as a walkie talkie with unlimited range.
I'm not really seeing the huge benefit here. If you work with others who don't follow such a protocol, set your Skype status to busy and you can't get calls. They'll then have to message you and you can initiate the callback if you're free. And is it really that much of an issue for people to establish calls immediately that there's a compelling need to auto-answer in a mannner that's different from Skype's auto-answer?
There's also the chicken and egg issue... nobody uses QuicklyChat and I can't see anybody I know jumping to use it given that everybody is already on Skype and it's 99% good enough with screensharing, full mobile support, forwarding to a phone number when unavailable, and so on. Plus, potential cross-talk issues: Facebook is likely preconfigured with a "green/ping me" setting but you may be in a Facebook video chat with someone when an auto-answer QuicklyChat session starts from their buddy... now your buddy is an unwanted third party in your Facebook chat. Awkward.