$re = '/(?s)(?=<)(?:(?=.*?<(?!.*?\1)(.*>(?!.*\2).*))(?=.*?>(?!.*?\2)(.*)).)+?.*?(?=\1)[^<]*(?=\2$)/';
$str = '<F<i<r<s>t>>> <<S><e><<c><o>><n>d> <<<<<<<Third>>>>>>>
<<123>,<456>,<789>>
';
preg_match_all($re, $str, $matches, PREG_SET_ORDER, 0);
// Print the entire match result
var_dump($matches);
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php