I don't see why not. Beats the heck out of toe-nailing!
The Simpson site shows plans using the Simpson Strong-Tie® 20-gauge Rigid Tie™ RTR connectors under the page //blog.strongtie.com/diy-suspended-garage-storage-shelves/. I the top brackets are different than this one. they are a corner bracket.
I used it to tie a 2X6 joist to 4X4 support worked great
I used them on a bottom rail of my greenhouse knee wall. I used landscape timbers for the post and the flat side on those timbers is what I nailed to. So, I do believe this would work for what you want them to do. They don't stick out at the edges of the 2x4.
I am not clear what type of "wall blocking" is being installed, but the RTR is not a load rated part and would not be recommended for structural applications (typically used in miscellaneous/DIY type projects). Thank you!
We did not use ours for an overhead placement. We had to build a new porch and platform and used it for the uprights that held the railing. They are strong, and were perfect for what we needed. Not sure about overhead storage.
The RTR is not a tested/load rated product. It would be up to the Designer/Engineer of Record to specify the appropriate connector based on framing layout, demand loads, local building codes, etc. Thank you!
There are no restrictions against installing the RTR vertically. Please note this product is not load rated; it would be up to the Designer to evaluate the suitability of the connector for the specific application. Thank you!