First of all, make sure you burn the discs in UDF format instead of ISO-9660 format. ISO-9660 only supports files up to 2 gibibytes or 4 gibibytes depending on the implementation.
UDF format doesn't seem to have a lot of base overhead for a volume with one file in it, but let's use a figure of 10 mebibytes of overhead (10×10242 bytes or 5120 DVD-sized sectors), to allow for faults in the writing process and plenty of room for the filesystem just in case.
(Capacity values quoted from http://en.wikipedia.org/wiki/Dvd#Capacity .)
DVD-R single layer
2,298,496 sectors, 4,707,319,808 bytes
subtract 10MiB overhead = 4,696,834,048 bytes
DVD+R single layer
2,295,104 sectors, 4,700,372,992 bytes
subtract 10MiB overhead = 4,689,887,232 bytes
DVD-R dual layer
4,171,712 sectors, 8,543,666,176 bytes
subtract 10MiB overhead = 8,533,180,416 bytes
DVD+R dual layer
4,173,824 sectors, 8,547,991,552 bytes
subtract 10MiB overhead = 8,537,505,792 bytes
So, if you are using any single layer discs (or might switch between +R and -R), then the 7-Zip command line would be:
7za a -v4689887232b FOLDER.7z FOLDER