You can use the "Babysitter" feature in the Edit Family dialog to indicate that two family members should never be scheduled together. The feature is located just below the list of volunteers in the Edit Family dialog. It is called the "Babysitter" feature because it is often used for two parents when they have a young child. Turning the option on for both parents will ensure that one parent is always left unscheduled so that they can be home with the child.
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