The links you find in the To-Do section of the Explorer Bar (left side under HOME) will vary depending on how many times you have used Express Accounts, if you are scheduled to run recurring payments or invoices, or if Express Accounts thinks it is time to back up your data. It's like Windows' quick access feature but can't be configured manually at this time.
You could send a suggestion regarding this here: https://www.nch.com.au/suggestions/