The new diiodine basicity scale pK(BI2) is quasi-orthogonal to most known Lewis basicity scales (hydrogen-bond, dative-bond and cation basicity scales). The diiodine basicity falls in the sequence N>P≈Se>S>I≈O>Br>Cl>F for the iodine-bond acceptor atomic site and SbO≈NO≈AsO>SeO>PO>SO>C=O>-O->SO(2) or PS≫-S->C=S≫N=C=S for the functionality of oxygen or sulfur bases. Substituent effects are quantified through linear free energy relationships, which allow the calculation of individual complexation constants for each site of polybases and thus the classification of aromatic ethers as carbon π bases and of aromatic amines, thioethers and selenoethers as N, S and Se bases, respectively. The pK(BI2) values of nBu(3)N(+)-N(-)C≡N, 2-aminopyridine and 1,10-phenanthroline reveal a superbasic nitrile, a hydrogen-bond-assisted iodine bond and a two-centre iodine bond, respectively. The diiodine basicity scale is a general inorganic but family-dependent organic halogen-bond basicity scale because organic halogen-bond donors such as IC≡N and ICF(3) have a stronger electrostatic character than I(2). The family independence can be restored by the addition of an electrostatic parameter, either the experimental pK(BHX) hydrogen-bond basicity scale or the computed minimum electrostatic potential.

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The diiodine basicity (a soft Lewis basicity) of 15 azoles (imidazoles, pyrazoles and triazoles) was measured by means of the formation constant of the diiodine-azole complexes in heptane at 298 K. The preferred sites of diiodine fixation are the nitrogens N-3 in imidazoles, N-2 in pyrazoles and N-4 in 1,2,4-triazoles. The diiodine basicity decreases with (i) the number of ring nitrogens, (ii) benzofusion, (iii) field electron-withdrawing effects of substituents on N-1 and (iv) for pyrazoles only, steric effect of substituents on N-1. In imidazoles and 1,2,4-triazoles, the lengthening and branching of alkyl groups on N-1 increase significantly the basicity, and 1-(adamant-1-yl)imidazole is the most basic of the azoles studied.