Suppose I want to use these two devices to set up a point-to-point connection. One device would connect to the existing subnet (via WLAN), the other device would connect directly to a computer (via LAN). Would this work?

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This is exactly what it is intended for, among other things.
Please note: If the circuits are connected to different fuses, the transmission can be very poor or even impossible.
There are so-called phase couplers, but my electrician didn't know what they were.

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Question about Devolo Magic 2 WiFi 6 Starter Kit

Suppose I want to use these two devices to set up a point-to-point connection. One device would connect to the existing subnet (via WLAN), the other device would connect directly to a computer (via LAN). Would this work?