Magnetic alignment and quadrupolar/paramagnetic cross-correlation in complexes of Na with LnDOTP5−

► Quadrupolar/paramagnetic cross correlation can lead to differential linebroadening and double-quantum coherences. ► LnDOTP5− complexes align in the magnetic field due to the anisotropic susceptibility of lanthanides. ► Both mechanisms are observed via 23Na NMR in solutions of sodium ions and LnDOTP5− complexes.