Engineering Soluble Diketopyrrolopyrrole Chromophore Stacks from a Series of Pd(II)-Based Ravels.

A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd L three-ring, a heteroleptic Pd L L' ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd L triple and a Pd L quadruple stack), were obtained and systematically investigated.

Frustrated flexibility in metal-organic frameworks.

Stimuli-responsive flexible metal-organic frameworks (MOFs) remain at the forefront of porous materials research due to their enormous potential for various technological applications. Here, we introduce the concept of frustrated flexibility in MOFs, which arises from an incompatibility of intra-framework dispersion forces with the geometrical constraints of the inorganic building units. Controlled by appropriate linker functionalization with dispersion energy donating alkoxy groups, this approach results in a series of MOFs exhibiting a new type of guest- and temperature-responsive structural flexibility characterized by reversible loss and recovery of crystalline order under full retention of framework connectivity and topology.

Rational Design of an Amphiphilic Coordination Cage-Based Emulsifier.

Self-assembled, porous coordination cages with a functional interior find application in controlled guest inclusion/release, drug delivery, separation processes, and catalysis. However, only few studies exist that describe their utilization for the development of self-assembled materials based on their 3-dimensional shape and external functionalization. Here, dodecyl chain-containing, acridone-based ligands (L) and shape-complementary phenanthrene-derived ligands (L) are shown to self-assemble to heteroleptic coordination cages cis-[Pd(L)(L)] acting as a gemini amphiphile (CGA-1; Cage-based Gemini Amphiphile-1).