Strong anisotropy of superexchange in the copper-oxygen chains of La_(14-x)Ca_(x)Cu₂₄O₄₁

Electron spin resonance data of Cu^{2+} ions in La_{14-x}Ca_{x}Cu_{24}O_{41} crystals (x=9,11,12) reveal a very large width of the resonance line in the paramagnetic state. This signals an unusually strong anisotropy of ~10% of the isotropic Heisenberg superexchange in the Cu-O chains of this compound. The strong anisotropy can be explained by the specific geometry of two symmetrical 90 degree Cu-O-Cu bonds, which boosts the importance of orbital degrees of freedom. Our data show the apparent limitations of the applicability of an isotropic Heisenberg model to the low dimensional cuprates.