An n-type semiconducting diazaporphyrin-based hydrogen-bonded organic framework.

Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and -nitrogen atoms.

Single-Crystal Structures of Benzenehexathiol and Its Disulfide Forms.

Oligothiols are useful as building blocks in the construction of disulfide-based macrocycles and polymers or as ligands for coordination polymers. Above all, benzenehexathiol () is a particularly important molecule, as it is used to construct conductive two-dimensional MOFs. Despite the desire to clarify its structure and isolate it to high purity, the chemical instability of has hampered single-crystal X-ray structure analysis of intact .

Deprotonation-Induced Color Modulation in N,N'-Dihydroxynaphthalenediimide-Based Organic Crystals.

N,N'-dihydroxy-1,4,5,8-naphthalenetetracarboxdiimide (NDI-(OH) ) has attracted much attention in recent years, because its doubly deprotonated state, (O-NDI-O) , has metal-coordination ability and characteristic electronic transition useful for designing electronic and optical functions. In contrast, a molecular crystal with the mono-deprotonated (HO-NDI-O) ion remains unknown. We herein report an organic crystal containing non-disproportionated (HO-NDI-O) ions, which are connected by very strong O-H-O hydrogen bonds.

An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals.

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni(NDI-Hpz)(dma)(NO)]·5DMA·HO (PMC-hexagon) (NDI-Hpz = ,'-di(1-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of HO molecules.

Preliminary chemical reduction for synthesizing a stable porous molecular conductor with neutral metal nodes.

Preliminary chemical reduction of naphthalenediimide (NDI)-based organic ligands was applied to the synthesis of a porous molecular conductor (PMC) with neutral metal nodes (cobalt(ii) acetylacetonate). The obtained semiconductive PMC (PMC-2) was stable due to the neutral metal nodes, providing an advantage over electrochemical reduction.