The Cover Feature shows the bis(tridentate Schiff base Pt(II)) complex containing dimethyl sulfoxide (Pt2L2DMSO) as a combination of yellow disks, gray disks, orange cones, and a black curved line. Pt2L2DMSO is unfolding due to the steric repulsion of the bulky ligand. The blue hexagons connected to the branched black lines stand for poly(4‐vinylpyridine) (P4VP). The green curved figure in the background indicates hybridization. The top image shows the hybridization of Pt2L2DMSO and P4VP, which causes a ligand exchange reaction for Pt2L2DMSO, forming a folding network structure in the yellow membrane. The yellow membrane exhibits red photoluminescence under ultraviolet irradiation (green wavy arrow). The reddish thunder expresses phosphorescence. The bottom image in the cover shows hybridization of Pt2L2DMSO and 4‐vinylpyridine (4VP), which causes a ligand exchange reaction for Pt2L2DMSO, forming the folding columnar packing structure in the brown block crystal. The black wavy arrow indicates non‐radiative deactivation. The metallofoldamer crystal does not exhibit solid photoluminescence under ultraviolet irradiation, while the metallofoldamer membrane is luminescent, thanks to the hybridization with P4VP. The background color changes gradually from orange to gray at the bottom to orange at the top, showing the improvement of photoluminescence from bottom to top. More information can be found in the Research Article by H. Achira and co‐workers.

A series of bis(tridentate Schiff base platinum) complex (Pt 2 L 2 ) linked with 2-methylenepropane-1,3-diyl were synthesized, and their photophysical properties were examined to analyze different solid states. X-ray crystallographic analysis indicated that Pt 2 L 2 containing 4-vinylpyridine (Pt 2 L 2 4VP) as a ligand had a helically-folded structure. It caused upfield chemical shifts and a redshift in UV-Vis absorption spectra compared to the analogous mononuclear complex. Pt 2 L 2 containing dimethylsulfoxide (Pt 2 L 2 DMSO) had no such helically-folded structure due to the steric repulsion of DMSO. Pt 2 L 2 4VP did not exhibit solid photoluminescence owing to the crystal packing. The mixture of poly(4-vinylpyridine) (P4VP) and Pt 2 L 2 DMSO (Pt 2 L 2 DMSOÀ P4VP) showed a similar redshift in UV-Vis absorption and excitation spectra to Pt 2 L 2 4VP, implying the helically-folded structure of Pt 2 L 2 with P4VP coordination. The Pt 2 L 2 DMSOÀ P4VP exhibited solid photoluminescence with a longer phosphorescence lifetime (2.4 μs) than the Pt 2 L 2 4VP crystals (0.5 μs), indicating regulated aggregation of the Pt 2 L 2 frames in the P4VP matrix.