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"Roll a D6 for each enemy unit that is within 1" of any affected units; on a roll of 6, the unit being rolled for suffers D3 mortal wounds"

Quoted right from the codex, but my question is does this only trigger once at the moment the Canticle is picked/rolled for at the start of the battle round?

Canticles last until they change. So when you roll Litany of the Electromancer any units in combat would immediately be rolled for and then any units that successfully charge would be rolled for.

Yeah thats what I figured. But my friend was pretty adamant about it only triggering at the start of the battle round and not triggering when one of my units got within an inch of one of his.