The ability of bromine containing anions of sulfophthalein dyes, such as bromophenol blue (BPB), bromocresol green (BCG), bromocresol purple (BCP), bromothymol blue (BTB), as well as non substituted phenol red (PhR), to form heteroassociates in aqueous solution was investigated. Singly and doubly charged anions BPB, BCG, BCP, BTB, and PhR (HAn -, An 2-) are capable of forming stable heteroassociates of composition Ct + •HAn -and (Ct + ) 2 •An 2-with cationic polymethine dyes (Ct + ), such as pinacyanol and quinaldine red. The enthalpies of formation of the dye ions and heteroassociates were calculated by semiempirical methods, and the most probable structure of heteroassociates was determined.Sulfophthalein dyes have long been effectively used as acid base and metallochromic indicators, and also as analytical reagents for photometric determination of many metal ions, surfactants, organic bases, etc. 1-4 The sulfo phthaleins possess a range of specific features, such as the possibility of the separate existence of anionic protolytic forms, their stability, weak dimerization, good resolution of absorption bands of singly and doubly charged ions in the electronic spectra and, as a result, the high color con trast of indicator transitions. 1,4-7 In this class of com pounds, bromo derivatives of sulfophthaneins (BDSP), such as bromophenol blue (BPB), bromocresol green (BCG), bromocresol purple (BCP), and bromothymol blue (BTB), have attracted attention. These BDSP are also used for the high precision in situ determination of pH of pure 8,9 and natural waters (a mixture of sulfophthaleins is used). 10,11 BDSP is the basis of sensitive elements of optical рН sensors, 12 fiber optic biosensors, and chips 13-16 (e.g., BTB and acetylcholine esterase doped with a sol gel film are sensitive to the content of organophosphate pesticide). 14 Indicators are effectively used for the study of serum albumin. 17-20 One of the most promising fields of application of BDSP as analytical reagents is the quanti tative determination of the range of components in bio agents and pharmaceuticals: antiviral (indinavir), 21 anti microbial (enoxacin), 22 antibacterial (gatifloxacin, 23 sparfloxacin, 24 ofloxacin 25 ), antihistaminic (oxomem azine), 26,27 and hypotensive (irbesartan, 28 nifedipine, 29 dilti azem 30 ) agents, antidepressants (tianeptine, 31 trazodone, 32 sertraline, fluoxetine, venlafaxine 33 ), antiulcer agents (raniti dine), 34 etc. 35,36 It is noteworthy that the high precision and rapid methods described above are based on the for mation of heteroassociates (ionic pairs) between the com ponent to be determined and the anionic forms of BDSP. Very often heteroassociates are extracted into an organic phase (tricloromethane, 21,22,25,27,29,30,32 dichlorometh ane 26,36 ). Let us note that solutions of BDSP are rather complex, since each of the dyes is subjected to many pro tolytic and tautomeric transformations (even in a thin film state BDSP can exist as an equilibrium mixture of associated lactone, quinoid, and zwitterionic form...