For 2024 the former marital status isn't relevant. As long as the divorce is final by December 31st both spouses are filing as single or head-of-household for 2024.
The maximum contribution limit for the HSA is limited by the coverage that the taxpayer carries. In this case, spouse 1 carries a high-deductible family plan and can contribute the maximum allowed in any year where they continue to carry that plan - whether they claim a deduction for the children covered by that plan or not.
Spouse 2 can claim the same deduction provided that they have a family plan as well. If all the members of the family are covered by the other plan, however, then spouse 2 is not eligible for a family plan and will have to take the lower deduction for the individual plan.
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