Just to make sure... the "key" should be ":" (unshifted press of the key) or "/" (shifted state of the key) ?
You've got it right except for this. You have to use the name of the key. The name of the key is different from the characters generated by the key. The name depends on your keyboard layout and the language setting of your operating system, so I can't tell it to you. HotkeyNet will show you the name on your PC if you press the key while looking in the upper right corner of HotkeyNet's screen. With most keys on most keyboards, the name stays the same whether shift is held down or not. You have to try on your keyboard and see.

<Hotkey AllMainKeys; shift AllMainKeys; Ctrl AllMainKeys>
<SendLabel w1, w2, w3, w4, w5>
<Key %Trigger%>
That looks fine. But you said "except" was involved somehow? Maybe you should paste your whole script here so I can see what's wrong and/or try it myself if necessary.