The Orbi has radio units for two bands, 2.4 and 5 Ghz. Both bands connect to the same internal software that provides the services needed to create a network for you. One of the functions is to assign an IP number to each device, regardless of which band, and to connect that IP to the IP provided by your Internet provider (ISP). So, each device in the network, regardless of the band, is in the SAME network. When you look at the Orbi for connected devices, it will show BOTH bands as BOTH bands are in ONE network. So, you see some on the 5ghz band, some on the 2.4ghz band, but ALL in ONE network.
Now, your thermostat should connect to the 2.4 Ghz band, get an IP as assigned by Orbi. Your iPhone will connect on whichever band is stronger, get an IP number from the same service in the Orbi. Thus, your iPhone will be able to "see" the thermostat eventually.
On the Orbi, you should be able to see in the list your iPhone, with an IP number, and each of your devices, including the thermostat, with their own IP number. All should be in the same network, i.e., 192.168.x.y, or 10.0.x.y, where the x and y will be in the range of 0 to 255. And any device in that range will be able to see any other device in that range. Typically the "x" is the same across all devices, but it could be, again, any number between 0 and 255. Typically it's 1, but it could be something else.
The only difference is that the 5Ghz band has higher speeds, but shorter range than the 2.4 Ghz band. The 2.4 has greater coverage, but slower speed. Also, 2.4 is better at penetrating walls, etc, than the 5 Ghz. The Orbis also have a backchannel where the individual units are constantly measuring the quality of the network and shifting from 2.4 to 5 based on quality of signal. Your 2.4 devices will have 0 quality on 5 Ghz, so they never get shifted to the 5 band. But any device with both may well be shifted based on the signal strength at any given moment.
The Orbi will not allow you to define which band any given device is attached to if it has dual-band capability. And, you cannot separate the 2.4 band and 5.0 band into two networks with the Orbi. Most folks don't need or want that separation, they just want to plug it in and let it do the sorting out of the devices. l used to have a router that allowed two networks and I did separate them but then discovered that the devices in one band didn't see the devices in the other, so I reconfigured the network to use both bands for ONE network and everything talked together just fine, irrespective of band.