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We’re in the process of updating the documentation for Zotero 5.0. Some documentation may be outdated in the meantime. Thanks for your understanding.
How can I save to or cite from a specific instance of Zotero when I have multiple copies open?
By default, when running multiple copies of Zotero (either by using multiple profiles or running Zotero in separate OS accounts), the Zotero Connector will save items to the first opened instance. To point a specific Zotero Connector installation to a specific Zotero profile, you can set the extensions.zotero.httpServer.port hidden pref in Zotero and the connector.url pref in the connector. Incrementing the port number by 1 for one pair (Zotero profile + connector installation) is sufficient.
At this time, it's not possible to point the word processor plugins to a specific instance of Zotero.