The tilaka - a mark/design on the forehead - has a long history in India. Vermilion and Kumkum/Sindoor (often reddened turmeric) are mentioned in old texts but so are facial designs made from pastes containing sandalwood (a particular favourite), musk and saffron. There is nothing definite to indicate that it was more than a cosmetic aid or that the design must be a red dot or that it denotes marital status in women.
By the 20th century of course in most orthodox Hindu communities sindoor denoted marital status (barring communities like the Brahmos and other reformist groups in the 19th/20th century) though modern variants are often used purely for decorative purposes.
The women-Meena Kumari, Rekha, Madhabi Mukherjee, Savitri and Raima Sen.