Inorganic-organic hybrid Cu-dipyridyl semiconducting polymers based on the redox-active cluster [SFe(CO)]: filling the gap in iron carbonyl chalcogenide polymers.

The construction of sulfur-incorporated cluster-based coordination polymers was limited and underexplored due to the lack of efficient synthetic routes. Herein, we report facile mechanochemical ways toward a new series of SFe(CO)-based dipyridyl-Cu polymers by three-component reactions of [EtN][SFe(CO)] ([EtN][1]) and [Cu(MeCN)][BF] with conjugated or conjugation-interrupted dipyridyl ligands, 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea), 4,4'-dipyridyl (dpy), or 1,3-bis(4-pyridyl)propane (bpp), respectively. X-ray analysis showed that bpee-containing 2D polymers demonstrated unique SFe(CO) cluster-armed and cluster-one-armed coordination modes the hypervalent μ-S atom.