UTF-8 does not define what “character” is so it depends on what you want. In this case, chars are Unicode scalar values, and so the first char of a &str is going to be between one and four bytes.
If you want just the first char, then don’t collect into a Vec<char>, just use the iterator:
let text = "hello world!";
let ch = text.chars().next().unwrap();
Alternatively, you can use the iterator’s nth method:
let ch = text.chars().nth(0).unwrap();
Bear in mind that elements preceding the index passed to nth will be consumed from the iterator.