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1) Use this 4-link gem setup that can stack the Wither debuff (applies 6% chaos damage taken per stack up to 15 stacks) on them:
Wither (blue) - Spell Totem Support (red) - Multiple Totem Support (red) - Faster Casting Support (blue)
They will take tons more damage this way - as long as the totems are up and firing the Wither skill at them. It is one of the most common methods to put some serious chaos DPS into bosses.
2) Apply the Despair curse on the boss. This could either come from you manually applying it through the Despair skill gem - through Hunter-influenced rings - or when in proximity of the enemy while using the Witchfire Brew flask. Do keep in mind that unique enemies / bosses have resistance to curses, making it less effective, but still worth using.
3) You can also opt for a helmet that has "Nearby enemies have #% to chaos resistance" which can be -9%. But this might be expensive / hard to craft when combined with other mods and such.
(Some?) Bosses take way less damage in the first 6 seconds of a fight. This is to counteract miners and trappers pre-stacking damage. This means that you shouldn't trigger stuff with cooldown or cooldown like properties (e.g. vaal skills) too early, if you can't kill the enemy in that timeframe.
Not every chaos skill stacks. For example if you use Essence Drain, only one DoT from it will damage the enemy, no matter how often you cast it on them. Same for Caustic Arrow, the DoT area of that doesn't stack. Toxic Rain on the other hand does. This results in some skills needing a different scaling.
If you're actually poisoning enemies and are a close quarters combatant, you might want to consider adding Plague Bearer in some 1-3 slot item, it doesn't have/need much support gems if any (empower comes to mind) and feeds off of your poison damage dealt.