Here is a quick and dirty way to define an associative array in Smarty 🙂
[{ assign var='myArray' value='/[\s,:]+/'|preg_split:"Blue:blue.png,Black:black.png,Red:deep_red.png"}] [{section loop=$myArray name=item step=2}] [{assign var="midx" value=$smarty.section.item.index+1}] Key: [{$myArray[item]}] - Value: [{ $myArray[$midx] }]<br> [{/section }]