Unraveling Concomitant Packing Polymorphism in Metallosupramolecular Polymers

The phenomenon of polymorphism is ubiquitous in biological systems and has also been observed in various types of self-assembled materials in solution and in the solid state. In the field of supramolecular polymers, different kinetic vs thermodynamic self-assembled species may exist in competition, a phenomenon termed as pathway complexity. In these examples, the transient kinetic species often has a very short lifetime and rapidly converts into the thermodynamic product. In this work, we report a π-conjugated Pt(II) complex 1 that self-assembles in nonpolar medium into two competing supramolecular polymers with distinct molecular packing (slipped (A) vs pseudoparallel (B)) that do not interconvert over time in a period of at least six months at room temperature. Precise control of temperature, concentration, and cooling rate enabled us to ascertain the stability conditions of both species through a phase diagram. Extensive experimental studies and theoretical calculations allowed us to elucidate the packing modes of both supramolecular polymorphs A and B, which are stabilized by unconventional N-H···Cl-Pt and N-H···O-alkyl interactions, respectively. Under a controlled set of conditions of cooling rate and concentration, both polymorphs can be isolated concomitantly in the same solution without interconversion. Only if A is annealed at high temperature for prolonged time, does a slow transformation into B then take place via monomer formation. Our system, which in many respects bears close resemblance to concomitant packing polymorphism in crystals, should help bridge the gap between crystal engineering and supramolecular polymerization.