Just so you know where my advice is coming from, I've built a few terrariums- largest is 16x16x26, and a few very small (1~3 gallon) aquariums. I've never made anything quite this big, not rectangular, nor holding anywhere near this amount of water.
There are lots of glass thickness calculators for rectangular tanks, but I haven't seen a hex one. You could find an appropriate sized hex tank and measure the thickness. Err on the side of caution. I won't even make a guess, being wrong can be messy.
Can you cut the glass yourself? My glass is all salvaged from old slider windows, if you aren't picky about the size you could possibly do the same for free/cheap at the cost of time. Though you might need glass that's thicker than available scrap windows. I think buying and repairing old tanks is typically cheaper than building it yourself, unless you happen to have free materials, but not as satisfying
I don't think a frame is necessary while curing. I've just used a couple small pieces of duct tape on the outside while curing the silicone. You'll probably want a friend to help put it together for an extra pair of hands though.
I use the house brand clear silicone from Home Hardware. It's in green and white containers, sold in 3 packs for $10, individually for $4(?), and says aquarium safe on it. You'll need a caulking gun to go with it, and make sure you get the 'clear' kind, not the 'white' kind. 1 tube would probably be enough, but it's so useful and doesn't go bad, and you would also cry if you ran out partway through the assembly that you might as well get extra.
My lights are so far pretty lame, just desk lamps resting on top. I do have some aluminum cladding (used to frame windows and doors) that I'll be building hoods out of at some point.
That's the best I can do, good luck!