Spin density distributions in molecular compounds containing unpaired electrons have been studied by polarized neutron diffraction (PND). The spin density distributions provide a unique perspective of the magnetic properties of the compounds. The background and fundamentals of polarized neutron diffraction are summarized in this review, followed by examples of applications in inorganic and organic chemistry. Spin densities in several compounds that are obtained by polarized neutron diffraction are highlighted. Spin densities in single molecular magnet [Fe 8 O 2 (OH) 12 (
tacn) 6 ] 8+ and cyano-bridged K 2 [Mn(H 2 O) 2 ] 3 [Mo(CN) 7 ] 2 ·6H 2 O demonstrate how to obtain magnetic interaction in the complexes by PND. PND studies of Ru(acac) 3 , containing one single unpaired electron, show small spin densities in this complex. Finally the use of PND in studying nitronyl nitroxide radicals is given. Our goal in this review is to illustrate how PND functions and how it serves as a sensitive tool in directly probing spin density in molecules.polarized neutron diffraction, spin (unpaired electron) density, paramagnetic, antiferromagnetic, magnetic structure factor 1 Background Unpaired electrons and magnetic properties of molecular compounds have been extensively studied by multiple spectroscopic methods. For instance, electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) have been used to determine electronic g-tensors and magnetic hyperfine interactions in paramagnetic compounds by employing the magnetic nuclei as local probes [1][2][3][4][5][6] . Since unpaired electrons usually reside in valence molecular orbitals, magnetic properties of the compounds that mainly arise from the unpaired electrons are very sensitive to changes in bonding. The spectroscopic properties, especially EPR, are particularly useful, providing information on the electron configuration of transition metals and spin density distributions in the molecules. While these techniques probe the energetic aspects of the wavefunction and bonding, polarized neutron diffraction (PND) examines the spatial aspects of the wavefunction and bonding in the compounds, giving different features of the bonding. PND is a unique technique in that it directly provides spin density in a compound.