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I set this in our dev environment (2021 R2 P10) on a chat workgroup and it did appear when the agent connected to the chat. It looks like the handler responsible for getting this custom attribute from directory services is GetIWebString in the AcdProcessEventInteraction handler and the attribute that is set is Eic_AgentConnectedMsg . You should be able to trace this out by debugging that handler and looking at the IP log to see why the attribute is or is not updating.
When I initially tested it, I had a minor typographical error that prevented it from working. I can confirm that it is CHAT TEXT:ACD Agent Connected
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