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so... you're building a miniature greenhouse.
The problem is insolation. technically, that's just light that hits the earths surface.... but in this context, it's light that passes through your glass chamber. it then hits whatever is inside and turns into heat, causing things to heat up.
Like a car in full sun. This would likely increase your thermal gains and not decrease them. (because for the gas mix or whatever inside the layer to have any effect... light already needs to be entering the system.)
Alternatively several things can be done to reduce solar heating. The first is painting your building a white (or very light color- sky blue, sandy tan, etc. titanium white is best... but... really who wants a stark white house like that?) Another is planting things. Trees in the yard will transpire- they release water into the atmosphere as part of photosynthesis which is why tree-shade feels cooler than blocked-sunlight-shade.
Then there's the living-roof set up. Basically you have some type of water barrier, then you have a large grow box (think of it like having a raised-bed garden tall enough and large enough to live under,) In which you plant... stuff. I recomend talking with whatever DNR-type you have (most state DNR's in the US, at least, have 'native seed mixes' you can buy by. my state has a wildflower mix that's... not entirely "weeds"....heh.)
Along that line of living roofs; you might be inclined to find some type of leafy climbing vine- Stay away from kudzu, it's horribly invasive, and I'd suggest staying away from non-native ivies as well. (though, those may be less offensive.) These plants will also transpire, and have the added benefit of absorbing and using the light as something other than heat.
If you don't like the idea of your house covered in vines... you could also go with a living wall There's lots of options there... some of them easier and more maintenance free than others. (you can also grow vegetables or whatever here, if you should like.)(you can do them indoors, too, for a natural air-purifier... anything leafy works.)
So essentially while trying to build an anti-green house I ended up building a normal green house. But that's actually exactly the answer I was looking for, thank you a lot! It was not so much about the practicality or whether there are better solutions but about whether I am missing something. (My other guess was that this light reflection would only work in the stratosphere to begin with.)
I'm a millennial living in a rented apartment so I cannot/could not implement anything. But we do indeed have trees in front of our windows, we have heat exchangers in two out of three rooms, PV on the rooftop and the house (built in 1900) is painted white (apart from the roof). Needless to say AC isn't a thing in my country. Currently we have slightly under 26°C in our apartment. And my parents have a (very white) house with what you call a living roof, that's a great name for that which I wasn't familiar with before. Again, thanks!