In September 1951, H. S. Gutowsky, D. W. McCall, and C. P. Slichter reported experiments on , , and , where they explained the presence of multiple resonance lines with an interaction of the form .
Independently, in October 1951, E. L. Hahn and D. E. Maxwell reported a spin echo experiment which indicates the existence of an interaction between two protons in dichloroacetaldehyde. In the echo experiment, two short, intense pulses of radiofrequency magnetic field are applied to the spin ensemble at the nuclear resonance condition and are separated by a time interval of τ. The echo appears with a given amplitude at time 2τ. For each setting of τ, the maximum value of the echo signal is measured and plotted as a function of τ. If the spin ensemble consists of a magnetic moment, a monotonic decay in the echo envelope is obtained. In the Hahn–Maxwell experiment, the decay was modulated by two frequencies: one frequency corresponded with the difference in chemical shift between the two non-equivalent spins and a second frequency, J, that was smaller and independent of magnetic field strength ( = 0.7 Hz).
Such interaction came as a great surprise. The direct interaction between two magnetic dipoles depends on the relative position of two nuclei in such a way that when averaged over all possible orientations of the molecule it equals to zero.
In November 1951, N. F. Ramsey and E. M. Purcell proposed a mechanism that explained the observation and gave rise to an interaction of the form I·I. The mechanism is the magnetic interaction between each nucleus and the electron spin of its own atom together with the exchange coupling of the electron spins with each other.
In the 1990s, direct evidence was found for the presence of J-couplings between magnetically active nuclei on both sides of the hydrogen bond. Initially, it was surprising to observe such couplings across hydrogen bonds since J-couplings are usually associated with the presence of purely covalent bonds. However, it is now well established that the H-bond J-couplings follow the same electron-mediated polarization mechanism as their covalent counterparts.
The spin–spin coupling between nonbonded atoms in close proximity has sometimes been observed between fluorine, nitrogen, carbon, silicon and phosphorus atoms.