I have auto-login enabled for my iChat accounts, and yet sometimes I start iChat wanting only some of the accounts to go online. Instead of quickly logging off those accounts I don't want logged in, I hold down the Shift key while iChat is starting. This disables auto-login for that session only -- the general preference is still intact, and the next time you start iChat (without using the Shift key), your accounts will auto-login as normal.
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