A glide before a vowel is easy to say and awkward to write, and Slavonic writing has taken three different approaches to it, all of them still visible.
The first is a dedicated letter for the sequence. That is what the iotified series is: single signs for the glide plus a, the glide plus e, the glide plus u and the glide plus each of the two nasal vowels. Several of them are transparently ligatures of a glide sign and a vowel letter, so the method is really a shorthand for the second approach rather than a separate principle.
The second is to write the two elements separately, glide sign plus vowel letter, which the manuscripts also do, inconsistently, alongside the ligatures.
The third emerged much later and is what the modern alphabets use. The iotified letters were reinterpreted: instead of meaning glide plus vowel, they came to mean either glide plus vowel at the start of a syllable, or plain vowel with a soft consonant in front of it. One sign, two readings, determined by position. That reinterpretation is what allowed Russian to write consonant softness without adding any diacritics to the consonants.
The shift is a good example of how a writing system changes without anyone deciding to change it. Nobody redefined these letters. The sound system moved underneath them, the letters went on being written in the same places, and their meaning was re-derived by readers from where they found them.