Experimental evidence of Bond‐angle and Hybridisation Alteration caused by π‐electron density alternation

X‐ray analyses of chain‐shaped and of coupled polymethines show an enlargement of the bond angles of the positively charged methine atoms and a contraction of the bond angles of the negatively charged methine atoms. The bond angle alteration can be explained by deviations from the trigonal hybridisation of the methine atoms. There exists a simple linear function between the square of the hybridisation parameter λ and the total charge densities calculated by means of the CNDO/2 method: λ2 ≅ 2 – Q.