RESUMO
Frequently encountered in crystalline materials, aromatic embraces (AEs) are formed when arylated molecules interact through multiple concerted aromatic interactions. AEs are a robust motif that is suitable for the preparation of amorphous bulk supramolecular polymers (BSPs). Crystal engineering revealed that the polymorphic compound (PPh3 )(Cp)Fe(CO){CO(CH2 )5 CH3 } (Cp=cyclopentadienyl), known as FpC6 , assembled into various chain structures through several AE motifs. Upon melting, FpC6 always adopted the same AE motif, which extended into the corresponding embracing "ladder" chains. The resultant BSP displayed typical polymer behaviour, including the presence of a glass transition and viscoelasticity, which allowed the effect of thermal history on the polymerisation behaviour to be explored. The ladder chains formed by the AE remain assembled at temperatures of up to 130 °C and were able to effectively suppress crystallisation during cooling. The ability of the AE to form chains at high temperatures and suppress crystallisation is a new opportunity to advance the field of BSPs and supramolecular chemistry.
RESUMO
The effect of chain structure on flexibility and stability of macromolecules containing weak P-Fe metal coordination bonds is studied. Migration insertion polymerization (MIP) of FpCX Fp (1) and PR2 CY PR2 (2) (Fp: CpFe(CO)2 ; CX and CY : alkyl spacers; P: phosphine; R: phenyl or isopropyl) generates P(1/2), in which the P-Fe and Fe-P bonds with opposite bonding direction are alternatively arranged in the backbone. On the other hand, P(FpCX P) synthesized from AB-type monomers (FpCX P) has P-Fe bonds arranged in the same direction. P(1/2) is more rigid and stable than P(FpCX P), which is attributed to the chain conformation resulting from the P-Fe bonding direction. In addition, the longer spacers render P(1/2) relatively flexible; the phenyl substituents, as compared with the isopropyl groups, improves the rigidity, thermal, and solution stability of P(1/2). It is therefore possible to incorporate weak metal coordination bonds into macromolecules with improved stability and adjustable flexibility for material processing.
RESUMO
PPh3CpFe(CO)(CO)(CH2)5CH3 (FpC6) spontaneously forms supramolecular polymers in the solid state. The polymers crystallize slowly over a period of one month and can be recovered by melting the crystals at 65 °C. The rheological profile of FpC6 fits the Maxwell model indicating the presence of chain entanglement. Crystal analysis reveals that FpC6 is able to assemble, via cooperative π-π interactions and weak C-H···O hydrogen bonding, into a duplex chain structure with truss arrangement of iron atoms. Powder X-ray diffraction (PXRD) of the polymers shows a double-peak pattern, characteristic for duplex ladder polymers. FTIR/ATR analysis further supports that carbonyl groups are involved in C-H···O hydrogen bonding responsible for the self-assembly. This discovery opens up new design motifs for organometallic supramolecular polymers.
RESUMO
Building on established supramolecular chemistry, metal coordination and organometallic chemistry have been widely explored for supramolecular polymers and nanostructures. Increasingly, research has demonstrated that this approach is promising for the synthesis of novel materials with functions and properties derived from metal elements and their coordination structures. Unique self-assembling behaviour and unexpected supramolecular structures are frequently discovered due to multiple non-covalent interactions in addition to metal coordination. However, an explicit understanding of the synergistic effects of non-covalent interactions for designed synthesis of metal containing assemblies with structure correlated properties remains a challenge to be addressed. Recent literature in the area is highlighted in this review in order to illustrate newly explored concepts and stress the importance of developing well understood and controlled supramolecular chemistry for designed synthesis.