Linear Copper Complex Arrays as Versatile Molecular Strings: Syntheses, Structures, Luminescence, and Magnetism

The defined linear arrangement of metal atoms in discrete coordination complexes or polymers is still one of the most intriguing challenges in synthetic chemistry. These chain arrangements are of fundamental importance, because of their potential applications as molecular wires and single molecule magnets (SMM) in microelectronic devices on a molecular scale. Oligonuclear Group 11 metal complexes with suitable bridging ligands, specifically those that are based on copper as the first choice of a cheap precursor coinage metal, are of particular interest in this regard. This is due to the superior luminescence properties of these linear clusters that often show d¹⁰ ⋅⋅⋅d¹⁰ interactions in their molecular structures. The combination of CuI with heavier coinage metal ions results in tunable emissive arrays that are also stimuli-responsive. Thus, both linear multinuclear CuI and linear heteropolymetallic CuI /AgI as well as CuI /AuI clusters are excellent candidates for applications in molecular/organic light-emitting devices (OLEDs). Alternatively, paramagnetic multinuclear cupric arrays are prominent as potential molecular wires with enhanced magnetic properties through multiple coupled d⁹ centers. This Review covers the whole range of linear multinuclear assemblies of cuprous and cupric ions in complexes and coordination polymers, their syntheses, photophysical behavior, and magnetic properties. Moreover, recent advances in the rapidly progressing field of hetero-CuI /AgI and CuI /AuI molecular strings are also discussed.