An anthracene-containing meso-fused carbaporphyrin, which has extended π-conjugation pathways as compared to the corresponding naphthalene-containing carbaporphyrin, has been synthesized. The weak global aromaticity of the anthriporphyrin also allowed its use as the diene for a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD). The resulting phlorin contains an interesting bicyclic structure. Moreover, to the best of our knowledge, this phlorin is the first Diels-Alder adduct of a diene forming part of the global π-conjugation pathway of an aromatic porphyrinoid.

The first fully connected aromatic carbaporphyrin dimer (6) and its bis-Pd complex (6-Pd 2 ) that bear a rigid naphthalene motif as an internal strap were synthesized. These dimers consisted of two aromatic carbaporphyrins that shared a naphthalene motif. The π-electron conjugation of the obtained macrocycles was proposed to have two separated local 22 π-electron pathways and a 34 π-electron pathway. Their weak aromaticity was fully supported by 1H NMR spectroscopy, NICS values, ACID calculations, and ICSS plots.

Various pyrene derivatives were synthesized and systematically examined in micelles. Synthesized mono and bispyrene derivatives were tested in micelles so that they displayed a strong excimer band and the excimer band was quenched in the presence of TNT and RDX. In the optimized condition, the binding constant for TNT of a simple dipyrene derivative 4 was increased up to 1.0 × 10 6 M −1 in cetyl trimethylammonium bromide (CTAB) micelles, which allowed for the detection of 2 ppb of TNT and 334 ppb of RDX by fluorescence titrations.

Allyliporphyrin is a carbaporphyrin that has replaced one pyrrole with an allyl group. Dynamic behavior (bond rotation) was observed by variable temperature H NMR and 2D-NOESY NMR spectroscopy and theoretically examined by DFT calculations. These studies revealed that well-defined bond rotation was first observed in the limited space of the carbaporphyrin from 2 through cis-2 and the calculated rotational barrier was low enough, with the relative energy level of cis-2 only 0.65 kcal mol higher than 2. The synthesized allyliporphyrin (2) is a strongly aromatic macrocycle as indicated by the chemical shifts of its inner NH and CH signals. However, its palladium complex displayed reduced aromaticity due to the tilted thiophene of Pd-2.

Cl(-) transporters that bear a terminal ethynyl group were synthesized; they consist of non-pyrrolic hydrogen bond motifs such as phenolic OH, amide NH, and triazole CH. The ethynyl group of these non-pyrrolic analogs plays an important role in chloride efflux and they exhibit no significant cytotoxic activity.