In the search for porphyrinoids with a built-in cyclopentadienyl moiety (true carbaporphyrins), a rational synthesis of carbathiaporphyrin, the synthons, has been elaborated. The donors (C,N,S,N) in the porphyrinic core of carbathiaporphyrinoids are potentially of fundamental importance for generating organometallic complexes, as exemplified through formation of the palladium(II) complex.

32-Hetero-5,6-dimethoxyphenanthrisapphyrins-macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins-were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5-bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π-electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X-ray structural analyses, and supported by DFT calculations. Although protonation does not change their π-conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32-hetero-5,6-dioxophenanthrisapphyrins.

Fusion of the structural motifs 21,23‐dithiaporphyrin and acetylene yields the 18‐π‐aromatic [18]triphyrin(4.1.1) framework (see structure; C gray, N blue, S yellow). The butyne moiety that joins the two thiophene rings reveals a slight distortion from linearity, showing a bowlike deformation directed out of the macrocycle.

Dithiaethyneazuliporphyrin, the first contracted carbaporphyrinoid, has been synthesized; the molecule contains an azulene moiety embedded in the [18]dithiacarbatriphyrin(4.1.1) macrocyclic framework.

A variety of primary and secondary benzylic amines were oxidized efficiently to N-benzylidenebenzylamines and imines, respectively, using 2,7,12,17-tetrapropylporphycene (H(2)TPrPc) photocatalyst and blue light emitting diodes (LEDs). The photooxidation of 4-methoxybenzylamine in the presence of H(2)TPrPc and its tin(IV) complex Sn(TPrPc)Cl(2) was studied in detail in order to show that operating mechanisms can be different depending on the photosensitizer type. Two experiments involving solvent deuterium isotope effect and competitive quenching with DABCO provide evidence for the singlet oxygen mechanism as the major pathway in the H(2)TPrPc-catalyzed reaction and the predominance of the direct electron transfer from the photoexcited dye to the amine when the Sn(TPrPc)Cl(2) complex was used as a photocatalyst.