Anion Coordination of Organophosphate and Bis-monourea-Based Ligands Forms a Hydrogen-Bonded Organic Framework (HOF) and a Six-Stranded Helicate

Here, we describe the distinct different anion coordination behaviors of organophosphate (PhOPO 3 2– = A) and two bis-monourea-based ligands L1 {1,1′-(1,4-phenylene)bis(3-(4-nitrophenyl)urea)} and L2 {1,1’-([1,1’-biphenyl]-4,4’-diyl)bis(3-(4-nitrophenyl)urea)}. The shorter L1 forms a hydrogen-bonded organic framework (HOF), encapsulating the counter cations in its cavities. While the longer L2 forms a rare six-stranded helicate. The formation of these structures depends on the coordinative flexibility of organophosphate and monourea. Crystal structures show that the HOF is held together by a AU 3 node (U = monourea), while the six-stranded helicate is a water bridged node AU 6 (H 2 O) that highly resembles the hydrogen bonding loop in the crystal structure of the PTP1B-pTyr assembly. This work provides critical guidance for construction of novel anion-directed assemblies based on the biomimetic hydrogen bonding between organophosphate and bis-monourea-based ligands.