Heterole-Fused [20]- and [22]Smaragdyrins and Fused-Heterole-Bridged [20]- and [22]Smaragdyrin Dimers.

In order to examine the effects of the fused heterole on the electronic properties of aromatic and antiaromatic smaragdyrins, 2,3-thiophene- and 2,3-indole-fused [20]smaragdyrins were synthesized by Suzuki-Miyaura coupling and subsequent oxidative fusion reaction, and were reduced with NaBH4 to the corresponding [22]smaragdyrins. Fused-thiophene- and fused-pyrrole-bridged [20]- and [22]smaragdyrin dimers were also synthesized in the similar manner. The installed fused heteroles mitigate the paratropic ring current of the [20]smaragdyrin but exert only minor effects on the diatropic ring current of the [22]smaragdyrin.

Sub--benziporphyrin: a subcarbaporphyrinoid and its B complex with an unprecedented planar tridentate 14π-aromatic network.

Sub--benziporphyrins were synthesized by Pd-catalyzed cross-coupling of ,'-diboryl--benzitripyrrane with 9,10-bis(1,1-dibromomethylenyl)anthracene. Reaction of sub--benziporphyrin with PhBCl and triethylamine gave its B-phenyl complex as a tetracoordinate nonaromatic B complex. In contrast, the reaction with BBr and triethylamine furnished a neutral B porphyrinoid with a planar and triangular coordination as the first example, in which the -phenylene unit was partially reduced, allowing for the global 14π-aromatic circuit.

Oxidations of (2,2'-Diphenyl)ethylidene-Bridged Porphyrin Dimers.

Oxidation reactions of (2,2'-diphenyl)ethylidene-bridged porphyrin dimers were examined for the synthesis of (2,2'-diphenyl)ethylidene-inserted porphyrin arch tape dimers. These reactions provided, in addition to the target arch tape dimers, unexpected products such as a bicyclo[3.3.

A Doubly meso-α Linked N-Confused Porphyrin Tape Silver(III) Complex Comprising an Antiaromatic Pyrrolo[2,3-f]indole Segment.

The free base form of doubly meso-α linked N-confused porphyrin (NCP) tape 3 was successfully synthesized via Ir(I) mediated intramolecular coupling. The following silver complexation afforded the Ag(III) complex of doubly meso-α linked NCP tape 4. While 3 exhibited 38π aromatic characters, 4 exhibited not only 18π aromatic NCP-type characteristics but also a decent antiaromatic contribution of 12π pyrrolo[2,3-f]indole segment, as probed by NMR spectra, absorption spectra, and DFT calculations.