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I would prefer to be able to tell them that, alternatively they can send an email to:
[email protected]

Is this an option?
Bouncing status reflects groups.io's ability to deliver messages, not receive them. For example, if a subscriber's mailbox is full, it is possible for that subscriber to post messages to the group while being unable to receive. Establishing an "unbounce" address would not help situations like this and will only cause accounts to immediately start bouncing again.

In other words, it would be no more or less effective than replying to a Bounce Probe - which is exactly my point, just that it would be easy and more likely to get to the bounced Subscriber/Member.

I wasn’t trying to solve everything about this problem, just that in this case Bounce Probes often are not received and/or found by Subscribers/Members. Such a ‘command’ email address could be a more successful alternative to the Bounce Probe. It would not be a replacement for the Bounce Probe, just another tool to try (manual, for when automatic has failed).

Other aspects of the problem which even Bounce Probes also fail to remedy, such as a full mailbox, could maybe be addressed by including that explanation in the Bounce notices sent to Subscriber/Member and Owner, as well as in the Bounce Probe (and so notified, the Owner could include it in their private email outreach, perhaps with text suggested by Groups.io).