All perfect praise be to Allaah, The Lord of the Worlds. I testify that there is none worthy of worship except Allaah, and that Muhammad is His slave and Messenger.
Your husband should have asked the scholars before having sexual intercourse with his wife after he had divorced her thrice based on his belief that divorce in menses is not effective. Allaah Says (what means): {…so ask the people of the message if you do not know.}[Quran 16:43] Besides, the Prophet said: “Why did they not ask if they did not know; the cure for ignorance is to ask (someone who knows).” [Abu Daawood]
Therefore, it was not permissible for him to have sexual intercourse with his wife after the third divorce unless he acted according to the view of the scholars who are trustworthy in terms of knowledge and piety and who are of the opinion that this is not forbidden. That is because it is permissible for the common person to act according to the view of the scholars whom he asked and act according to the Fatwa that they issued to him.
Based on this, if he did not know the ruling and did what he did while being negligent in regard to asking the scholars, then he is sinful. However, if he was acting according to the view which he thought to be correct, then he is not sinful.
Allaah Knows best.