Why doesn't my F-Key Shortcuts setup work?

Any ideas why not?

Yep. From the Help Viewer topic "Creating keyboard shortcuts for applications"

"Note: You can create keyboard shortcuts only for existing menu commands. You cannot define keyboard shortcuts for general purpose tasks such as opening an application or switching between applications."

For your shortcut method to work, there would have to be an existing menu command in Finder to open the particular application, & you would have to enter that command exactly as on that menu in the Menu Title text box. (It isn't a description text box, it is the exact text that the OS matches to the text of the menu command to know which one to execute.)

Are there any "free" ways to assign the F-Keys to open Applications?

None I'm aware of. There are a number of utilities designed to do complex actions that are activated by 'triggers,' one of which can be a keystroke like an F-Key, but since they are designed to be powerful macro utilities, they aren't free.

If such things sound interesting, you can check out:

• Keyboard Maestro ($20) at http://www.keyboardmaestro.com/main/

• iKey ($30) at http://scriptsoftware.com/ikey/

• QuicKeys ($80) at http://www.cesoft.com/products/qkx.html

Each of these will allow you to assign an F-Key (or any other available hot key combination) to open an app, plus do much more.

I'm not sure what you mean by "something different." Many keyboard shortcuts, both those built into the system & into some applications, are invoked by F-Keys, alone or in combination with modifier keys. To that extent at least, they are keyboard shortcuts.

In any event, the "Keyboard Shortcut" pref option is not designed to map any keyboard shortcut to anything other than existing menu commands, with or without F-Keys. The previously mentioned macro apps do not have this limitation & would allow you to map these keys to launchng apps, including ones saved as AppleScript applications. Basically, that is what Speakable Items files that you write are.

Information for creating & using them can be found in the AppleScript section of Help Viewer & its links. (Try the topic titled "Running scripts from a spoken command" to get an idea of what's involved.)

However, I know of no other way of mapping these or any other executable files to F-Keys.

Please post your experiences with this app if you try it. From the documentation online, it appears to be very old & I have doubts about its compatibility with Tiger.