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My familiarity with multisigs is very limited, but from what I understand you'd think there would be a way or at the very least some sort of smart contract tool that could be developed if nothing else.

There should already be a simple app made that takes care of this in my opinion - A 'will executor' app. My wife wouldn't know what to do but I assume she could ask someone. It would be useful to have a template made of all important information and keys that could be locked away somewhere with instructions on what to do or, who they can trust. There are people on Steem I would trust to help my wife.