As others have mentioned in the comments, you cannot have duplicate key's in a dictionary, Python knows to update the existing key with the latest value it's been set to in the duplicate declarations.
You could have a Dictionary that has a tuple (immutable), or list (mutable) as its value.
So if you wanted to have the following coupled information:
'Ah', 'As', 'Ac', 'Ad' , 'Kh', 'Ks' ...
You could represent that data with:
d = { 'A' : ('h', 's', 'c', 'd'), 'K' : ('h', 's') }
A list value can also work if you wanted to mutate the data within the list. (or set if you do not want duplicate values)
d = { 'A' : ['h', 's', 'c', 'd'], 'K' : ['h', 's'] }
This way you have essentially factored out your common character to be your key.