5,10,15,20-Tetrakis-3,5-di-tert-butyl-4-oxocyclohexadienylidene porphyrinogen and its di-N-benzylated derivative are solvatochromic dyes capable of binding anionic species. The influence of solvent polarity and hydrogen bonding on their electronic absorption spectra was observed. Hydrogen bonding by the porphyrinogen amine protons of acetone solvent molecules could be observed in the solid state. The acetone solvate of N21N23-dibenzyl-5,10,15,20-tetrakis-3,5-di-tert-butyl-4-oxocyclohexadien ylidene porphyrinogen crystallized under anhydrous conditions in the space group P (1) over bar with cell dimensions a = 12.1693(11)angstrom, b = 17.5849(13)angstrom, c = 21.0965(17)angstrom, alpha = 69.870(4)degrees, beta = 78.140(4)degrees, gamma = 82.865(5)degrees. These porphyrinogens are capable of binding a variety of anions and can be used to distinguish fluoride chromogenically from the other halide anions. Solvatochromism was combined with anion binding in an attempt to provide more selective tests for anions. The anion binding properties were investigated using UV/vis spectrophotometry and H-1 NMR spectroscopy.