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Abstract The assembly of cluster-based π-stacked porous supramolecular frameworks presents daunting challenges, including the design of suitable cluster building units, control of the sufficient C-H···π interactions, trade-off between structural dynamics and stability as well as understanding the resulting collective properties. Herein, we report a cluster-based C-H···π interaction-stacked porous supramolecular framework, namely, Cu12a-π, consisting of Cu12 nanocluster as a 6-connected node, which is further propagated to a dynamic porous supramolecular frameworks via dense intralayer C-H···π interactions, yielding permanent porosity. In addition, Cu12a-π can be transformed into cluster-based nonporous adaptive crystals (Cu12b-NACs) via ligand-exchange following a dissociation-reassembly mechanism. Moreover, Cu12a-π can efficiently remove 97.2% of iodine from saturated iodine aqueous solutions with a high uptake capacity of 2.96 g·g−1. These prospective results positioned at cluster-based porous supramolecular framework and enlighten follow-up researchers to design and synthesize such materials with better performance.

FeCl3-mediated oxidative cyclization was successfully used to construct an extended thiophene-pendant pyrene skeleton and synthesize a novel thiophene-fused polycyclic aromatic (THTP-C) with a tetracene core. The identity of the compound was confirmed by 1H-NMR, 13C-NMR, MS, and elemental analysis. Meanwhile, a single crystal of THTP-C was obtained and analyzed by X-ray single-crystal diffraction. THTP-C has a “saddle” shaped π-conjugated 1-D supramolecular structure, and favors highly ordered self-assembly by π-π interactions as evidenced by its concentration-dependent 1H-NMR spectra in solution. The optical properties of THTP-C were investigated by ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy and its electrochemical properties were investigated by cyclic voltammetry (CV). The relatively large band gap (2.86 eV), low EHOMO level (−5.64 eV) and intermolecular π-π interactions imply that THTP-C has a high stability against photo-degradation and oxidation, and may be a promising candidate for stable hole-transporting materials.

The asymmetric unit of the title compound, C28H20N2O2·0.5C2H5OH, contains two independent molecules of 1,1′-[o-phenylenebis(nitrilomethylidyne)]di-2-naphthol, denoted A and B, and one ethanol solvent molecule. The hydroxy groups are involved in intramolecular O—H...N hydrogen bonds influencing the molecular conformations, which are slightly different in molecules A and B, where the two bicyclic systems form dihedral angles of 51.93 (9) and 58.52 (9)°, respectively. In the crystal structure, a number of short intermolecular C...C contacts with distances of less than 3.5 Å suggest the existence of π–π interactions, which contribute to the stability of the crystal packing.

The title compound, C34H25Cl3O3S2·0.5CH3OH, was synthesized by the reaction of thiophene-2-carbaldehyde with acetophenone and NaOH under solvent-free conditions, using tetrabutylammonium bromide as a phase-transfer catalyst. The central six-membered ring adopts a chair conformation with the bulky thiophene, 4-chlorophenyl and 4-chlorobenzoyl substituents in equatorial positions. The hydroxyl group is in an axial position and forms an intramolecular O—H...O hydrogen bond to the carbonyl group of an adjacent 4-chlorobenzoyl substituent. The methanol solvent molecules are disordered equally over two positions within one-dimensional channels, with site occupancy factors of 0.25.

The asymmetric unit of the title compound, C19H16O2S2, contains two independent molecules with slightly different conformations. In the crystal structure, weak intermolecular C—H...O hydrogen bonds [C...O = 3.279 (15) and 3.407 (16) Å] link the molecules into chains extended along the c axis.

The title complex, bis(μ-benzene-18-crown-6)-3κ6O:4κO;4κ6O:3κO-bis(benzene-18-crown-6)-1κ6O,6κ6O-tetra-μ-thiocyanato-1:2κ2S:N;2:3κ2N:S;4:5κ2S:N;5:6κ2N:S-dithiocyanato-2κN,5κN-2,5-dicopper(I)-1,3,4,6-tetrapotassium(I), [K4Cu2(NCS)6(C16H24O6)4] or {[K(C16H24O6)]4[Cu(NCS)3]2}, consists of four [K(benzene-18-crown-6)]+ cations and two [Cu(NCS)3]2− anions, forming a dimeric structure with site symmetry overline{1}. In each [Cu(NCS)3]2− anion, the CuI atom is coordinated by three N atoms of thiocyanate ligands in a trigonal–planar coordination geometry. Each [Cu(NCS)3]2− anion bridges two [K(benzene-18-crown-6)]+ cations, with K—S distances of 3.317 (3) and 3.198 (3) Å, and two [K(benzene-18-crown-6)]+ cations are linked across a crystallographic centre of inversion, with K—O distances of 2.903 (5) Å.

In the title compound, C23H16ClN, the crystal packing exhibits no significantly short intermolecular contacts. The benzene rings show a disrotatory arrangement and the angles between them and the pyridine ring range from 20.80 (3) to 37.56 (4)°. The Cl atom deviates by 0.01 (3) Å from the plane of the benzene ring to which it is attached.