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That image shows they are On Queue and the notification indicates they are not scheduled to be on queue. I.e., they either don't have a schedule, the schedule is not published, or the scheduled activity for the published schedule is not On Queue for the current period.
On queue status outside of scheduled shift times being considered an exception is governed by configuration setting noted below. The reason you would want this is to catch cases of agents coming in to work when they are not scheduled to be which is why the default is for it to be enabled.
Assuming the agent has the "Agent Schedule > View" permission, there is a published schedule, and they are scheduled to be on queue, but are off queue, then they should receive an out of adherence notification. It is not uncommon for an agent to say they don't receive, what is a guaranteed delivery because they ignore/dismiss.https://help.mypurecloud.com/articles/real-time-adherence-overview/ has an adherence mapping. Specifically for On Queue scheduled time their presence needs to be On Queue and we additionally look at their routing status as noted in the article in Notes section:
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