Vitruvius described its use as an artist's pigment in the first century BC. Sir Isaac Newton added Indigo to the spectrum of visible light to complete the symbolic number of seven spectral colours. The human eye is relatively insensitive to indigo's frequencies, and some otherwise well-sighted people cannot distinguish indigo from blue and violet. For this reason some commentators including Isaac Asimov have suggested that indigo should not be regarded as a colour in its own right but merely as a shade of blue or violet.
Field's Chromatography or Treatise on Colours and Pigments as Used by Artists
"Indigo or Indian Blue, was known to the ancients under the name of Indicum, whence its present appellation. In modern Europe, it first came into extensive use in Italy; but about the middle of the sixteenth century, the Dutch began to import and employ it in considerable quantity. Present in the woad plant, which is a native of Great Britain, indigo is chiefly derived from a genus of leguminous plants called Indigofera, found in India, Africa, and America. The colouring matter of these is wholly in the cellular tissue of the leaves, as a secretion or juice; not, however, in the blue state in which one is accustomed to see indigo, but as a colourless substance, which continues white only so long as the tissue of the leaf remains perfect: when this is by any means destroyed, oxygen is absorbed from the atmosphere, and the principle becomes blue. The best indigo is so light as to swim upon water, but the commercial article seldom contains more than 50 per cent of blue colouring matter or true indigo, the remainder consisting of either accidental or intentional impurities.
"In painting, indigo is not nearly so bright as Prussian blue, but it is extremely powerful and transparent, and may be described as a Prussian blue in mourning. Of great body, it glazes and works well both in water and oil. Its relative permanence as a dye has obtained it a false character of extreme durability as a pigment, a quality in which it is nevertheless very inferior even to Prussian blue. By impure air it is injured, and in glazing some specimens are firmer than others, but not durable; while in tint with white lead they are all fugitive. Employed in considerable body in shadow, it is more permanent, but in all respects Prussian blue is superior. Despite this want of stability, indigo is a favourite colour with many artists, who sacrifice by its use future permanence to present effect. It is so serviceable a pigment for so many purposes, especially in admixture, that its sin of fugacity is overlooked. Hence we find indigo constantly mentioned in works on painting, their authors forgetting or not caring to remember that wholesome axiom, a fugitive colour is not rendered durable by being compounded. Artistically, it is adapted for moonlights, and when mixed with a little lamp black, is well suited for night clouds, distant cliffs, etc. With a little raw umber and madder it is used for water in night effects. With the addition of a little madder it forms a good grey; and with madder and burnt Sienna is useful for dark rocks, this combination, with raw Sienna, being also eligible for boats. For these and other mixed tints, however, Prussian blue saddened by black with a suspicion of green in it, is equally fitted, and is more permanent. Indeed, it would be perhaps justifiable to introduce such a compound, under the name say, of Factitious Indigo.
"Indigo in dust, or in small bits, is often adulterated with sand, pulverized slate, and other earthy substances. That indigo is best which is lightest, brightest, most copper-coloured, most fine-grained, and inodorous."