Influence of the Substituent’s Size in the Phosphinate Group on the Conformational Possibilities of Ferrocenylbisphosphinic Acids in the Design of Coordination Polymers and Metal–Organic Frameworks

Abstract

This paper illustrates how the size and type of substituent R in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that H-phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers. It sheds light on how different reaction conditions and substituents can affect conformational possibilities and coordination packing, which could have significant implications for developing new polymers with unique properties.

Supramolecular Systems Linked to Metal‐Organic Frameworks

“…As a matter fact, a convenient method for preparing mono-and bisferrocenylphosphinic acids has been developed by the group of Khrizanforov, establishing a structural reference on the coordination of phosphorus atom and reaction conditions of bisferrocenylphosphinates. These structural ligands have an impact on the coordination polymers formation and presumably their inherent properties [75].…”

Evidence of extremely short hydrogen bond in the homoconjugated ferrocene-1,1′-diyl-bisphosphinic acid anion: sign change of the H/D isotope effect on the 31P NMR chemical shift

“…17–19 Besides, the conformational manifold of intra- and intermolecular hydrogen bonding patterns of Fc(P(R)OOH) 2 in conjunction with the substituent size in the phosphinate group have proven to be paramount for the coordination properties of Fc(P(R)OOH) 2 in novel coordination polymers and metal–organic frameworks with tunable optical, magnetic and redox properties. 20–24 Separate interest is drawn toward H-bonded complexes formed solely by Fc(P(R)OOH) 2 . Along with other phosphorus-containing acids (phosphinic, phosphonic and phosphoric), Fc(P(R)OOH) 2 species possess both proton-donating POH and proton-accepting PO moieties and are therefore inherently capable of forming H-bonded complexes of two types: electroneutral self-associates 25–27 and homoconjugated anions, 28–30 i.e.…”