An example of the data and an explanation of what you want to achieve would indeed have been useful. From your code, it would appear that the dates are stored as date strings and that if the date is the last day of the week, you want to make it the day before.
That is trivial to achieve. The exact equivalent of your code without a loop is simply:
wday = weekday(export.Expiration);
export.Expiration(wday == 7) = cellstr(datetime(datenum(export.Expiration(wday == 7) - 1, 'ConvertFrom', 'datenum', 'Format', 'MM/dd/yyyy'));
However, I would recommend that you actually store your date as datetime, which would make the date manipulation much easier and avoid this triple conversion to date number -> datetime -> date string:
export.Expiration = datetime(export.Expiration, 'InputFormat', 'MM/dd/yyyy', 'Format', 'MM/dd/yyyy');
islastday = day(export.Expiration, 'dayofweek') == 7;
export.Expiration(islastday) = export.Expiration(islastday) - 1;
I assume you're aware that in matlab, the last day of the week is Saturday. Otherwise you'll have to change the 7 to 1, if you meant to find the Sundays.