The halogen bonding has recently gained well deserved attention in present-day research for its importance in many fields of supramolecular science and crystal engineering. Although generally overlooked in comprehensive studies in the past, halogen bonding has become an important tool also in the field of materials science. An increased number of scientific reports are published every year where the halogen bonding is exploited in soft materials rather than in crystal engineering. Here, we focus on a description of the most exciting contemporary developments in the field of halogen-bonded functional soft materials, assembled using the guiding principles of crystal engineering. We give a particular emphasis to those published in the last few years.

Halogen bonding is an interaction of choice in supramolecular polymers for efficient light-induced surface patterning.

The structures of halogen-bonded infinite chains involving two diiodoperfluoroalkanes and a bent bis(pyrid-4′-yl)oxadiazole show that the geometry of the pyridyl pendant rings is translated into the angle between the formed halogen bonds.

Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen‐bonded supramolecular anions [C_nF_2 n+1‐I⋅⋅⋅I⋅⋅⋅I‐C_nF_2 n+1]⁻ are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen‐bonded liquid crystals, and 2) imidazolium‐based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.

It is demonstrated that halogen bonding can be used to construct low‐molecular‐weight supramolecular complexes with unique light‐responsive properties. In particular, halogen bonding drives the formation of a photoresponsive liquid‐crystalline complex between a non‐mesogenic halogen bond‐donor molecule incorporating an azo group, and a non‐mesogenic alkoxystilbazole moiety, acting as a halogen bond‐acceptor. Upon irradiation with polarized light, the complex exhibits a high degree of photoinduced anisotropy (order parameter of molecular alignment > 0.5). Moreover, efficient photoinduced surface‐relief‐grating (SRG) formation occurs upon irradiation with a light interference pattern, with a surface‐modulation depth 2.4 times the initial film thickness. This is the first report on a halogen‐bonded photoresponsive low‐molecular‐weight complex, which furthermore combines a high degree of photoalignment and extremely efficient SRG formation in a unique way. This study highlights the potential of halogen bonding as a new tool for the rational design of high‐performance photoresponsive suprastructures.