I don't believe it is true that harlequins have any form of toxin/venom. Infact it's been a long going myth for quite awhile.
My explainations are:
1. The starfish is immobilized due to the constant aggitation the shrimp cause while it is flipped upside down. The starfish naturally makes no sudden movements due to stress caused by the shrimp.
2. By memory, I cannot identify one single crustecean that is actually toxic. Seriously, when was the last time you've heard a lobster, crab, shrimp, etc as poisonous? I've heard them hosting in venomous entities (crown of thorns stars, urchins, anemones, etc) but never naturally born with a venom.. which makes me rule out hymenocera in possession of any toxin.
(I could be wrong about there being no such thing as a venomous, or poisonous crustecean, I'm sure out of the millions of species there might be a few, but I do not recall a single one let alone a much more well known species like harlequin shrimp)
3. Evidence... let's face it... we're in 2015 and we haven't even found any documents or images of a toxin being found by research institutions. I'm sure by now we'd confirm something if it's such a heavy debate. What we do have however is images of the animal's pereiopods which show very close up detail of the tips, without any indication of a "fang" or "injector". You can see these photos I'm refering too somewhere in
here.
5. Finally, from my experience, if I distract or remove a starfish from the harly's possession, off it goes. It is still active and moving around. Something that any injection would prevent the starfish from doing. Starfish do end up dying sometimes due to infection in the wounds, but otherwise, if it's moving perfectly fine, than either the venom is very inneffective, or just simply doesn't exist.
Now there is another possibility and explaination, which is when a harlequin consumes the invasive crown of thorns starfish (which is toxic) they it may pocess the toxin in their bodys. However this toxin would never be effective for the harlequin besides giving a fish a bad taste or fouling the water.