Nanographene-Fused Expanded Carbaporphyrin Tweezers.

A nanographene-fused expanded carbaporphyrin (5) and its BF2 complex (6) were synthesized. Single-crystal X-ray structures revealed that 5 and 6 are connected by two hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units, respectively. As prepared, 5 and 6 both show nonaromatic character with figure-of-eight carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized by a partially confined space between the two constituent HBC units. The distance between the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5 and 35.2° for 5 and 6, respectively. The interactions between 5 and 6 and fullerene C60 were studied both in organic media and in the solid state. Proton NMR spectral titrations of 5 and 6 with C60 revealed a 1:1 binding mode for both macrocycles. In toluene-d8, the corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M-1 for 5 and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the formation of 1:1 fullerene inclusion complexes in the solid state. The C60 guests in both complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed subpicosecond ultrafast charge separation between 5 (and 6) and C60 in the complexes. To the best of our knowledge, the present report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.

A Janus carbaporphyrin pseudo-dimer.

Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including 1H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond.

Facile Ligand Exchange of Ionic Ligand-Capped Amphiphilic Ag2S Nanocrystals for High Conductive Thin Films.

A surface ligand modification of colloidal nanocrystals (NCs) is one of the crucial issues for their practical applications because of the highly insulating nature of native long-chain ligands. Herein, we present straightforward methods for phase transfer and ligand exchange of amphiphilic Ag2S NCs and the fabrication of highly conductive films. S-terminated Ag2S (S-Ag2S) NCs are capped with ionic octylammonium (OctAH+) ligands to compensate for surface anionic charge, S2-, of the NC core. An injection of polar solvent, formamide (FA), into S-Ag2S NCs dispersed in toluene leads to an additional envelopment of the charged S-Ag2S NC core by FA due to electrostatic stabilization, which allows its amphiphilic nature and results in a rapid and effective phase transfer without any ligand addition. Because the solvation by FA involves a dissociation equilibrium of the ionic OctAH+ ligands, controlling a concentration of OctAH+ enables this phase transfer to show reversibility. This underlying chemistry allows S-Ag2S NCs in FA to exhibit a complete ligand exchange to Na+ ligands. The S-Ag2S NCs with Na+ ligands show a close interparticle distance and compatibility for uniformly deposited thin films by a simple spin-coating method. In photoelectrochemical measurements with stacked Ag2S NCs on ITO electrodes, a 3-fold enhanced current response was observed for the ligand passivation of Na+ compared to OctAH+, indicating a significantly enhanced charge transport in the Ag2S NC film by a drastically reduced interparticle distance due to the Na+ ligands.

Remotely Modulating the Optical Properties of Organic Charge-Transfer Crystallites via Molecular Packing.

Organic charge-transfer complex (CTC) formation has emerged as an effective molecular engineering strategy for achieving the desired optical properties via intermolecular interactions. By synthesizing organic CTCs with carbazole-based electron donors and a 7,7,8,8-tetracyanoquinodimethane acceptor and adopting a molecular linker located remotely from the charge-transfer interface within the donors, we were able to modulate near-infrared absorptive and short-wavelength infrared emissive properties. Structural characterizations performed by using single-crystal X-ray diffraction confirmed that the unique molecular arrangements induced by the steric hindrance from the remotely located linker significantly influence the electronic interactions between the donor and acceptor molecules, resulting in different photophysical properties. Our findings offer an improved understanding of the interplay between molecular packing and optoelectronic properties, providing a foundation for designing advanced materials for optoelectronic applications.