Regulating the dimensionality of diphosphaperylenediimide-based polymers by coordinating the out-of-plane anisotropic π-framework toward Ag +

The development of hetero-π-conjugated molecules is of significance for constructing diverse assembling superstructures based on heteroatom-related bonded or nonbonded interactions. Herein, we developed one-pot P-heteroannulation via palladium-catalyzed dual P—C bonds formation and subsequent sulfidation to construct two isomeric diphosphaperylenediimides ( cis - 5 and trans - 5 ). The unique out-of-plane anisotropic π-framework induced a cumulative anisotropy with a dipole moment of up to 8.82 D for cis - 5 , leading to distinct supramolecular packing arrangements. Optical and electrochemical characterizations demonstrated that they showed the largest redshifts extending to 574 nm and rather low-lying LUMO levels of −4.41 eV. Furthermore, the introduced P=S moieties endowed these diphosphaperylenediimides with prominent coordination ability towards Ag + , thus the first example of perylene diimide (PDI) core-involved metal-organic coordination polymers (MOCPs) with tunable dimensionality varied from 1D, 2D, to 3D were tactfully achieved. In view of easy accessibility and 2D layered porous structure, thus 2D ( trans - 5 )·(AgOTf) based MOCP showed high crystallinity and good CO 2 adsorption capacity with surface area of 112 m 2 /g. The result opens a span-new avenue for exploring rylene imide-based MOCPs and related properties by integrating P functionality.