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Princess Leopoldina was married on 15 December 1864 to Prince Ludwig August of Saxe-Coburg and Gotha, Duke in Saxony, second son of Prince August of Saxe-Coburg and Gotha and Princess Clémentine of Orléans, in Rio de Janeiro. Ludwig August (in Portuguese, Luís Augusto) and his first cousin, Prince Gaston, comte d'Eu, were sent to Brazil to marry the Emperor's daughters, Isabel and Leopoldina. The original arrangement was for Gaston to marry Leopoldina and Ludwig August to marry Isabel, but the sisters decided otherwise and their father agreed to their wishes, having himself experienced the unhappinesses of an arranged dynastic marriage. Ludwig August and Leopoldina married two months after the wedding of Isabel and Gaston. She was thus styled Princess Ludwig August of Saxe-Coburg and Gotha. She became a sister-in-law of Ferdinand I of Bulgaria.
Generations indicate descent from João IV, King of Portugal, formerly João II, Duke of Braganza, the first Braganza monarch of Portugal, until Manuel II, King of Portugal, the last monarch of Portugal, excluding the Miguelist line; italics indicate a head of the House