Chloro and Hydroxo Forms of a Boron(III) Subtriazaporphyrin Macrocycle

Abstract

cis-3,4-Dicyano-3-hexene undergoes cyclotrimerization with BCl3 to form the new subtriazaporphyrin chloro[hexaethylsubtriazaporphyrinato]boron(III). The hydroxo derivative of this macrocycle has also been made, and the X-ray crystal structure of the hydroxy form was determined. Electronic absorption and magnetic circular dichroism spectra of the hydroxo monomer species were interpreted using time-dependent density functional theory calculations.

Synthesis, Characterization, Molecular Structure and Theoretical Studies of Axially Fluoro‐Substituted Subazaporphyrins

“…Aromatic or p-conjugated curved compounds have been the object of many theoretical and experimental studies in recent years as a consequence of their intriguing chemical and physical properties. [1,2] Among them, subazaporphyrins [3][4][5][6][7] (SubAPs) are heteroaromatic chromophores that constitute the lower homologues of tetraazaporphyrins (phtha-Abstract: A new and general synthetic method for the preparation of fluorosubstituted subazaporphyrins is reported that involves the treatment of the corresponding chloro-or aryloxy-substituted subazaporphyrins (SubAPs) with BF 3 ·OEt 2 . The strategy has been applied to both subphthalocyanines (SubPcs) and subporphyrazines (SubPzs).…”

Perfluorinated Porphyrazines. 5. Perfluoro-a,b-dicyanostylbene: Molecular Structure and Derived (Sub)Porphyrazine Complexes with IIIa Group Elements

“…with pyrazine [22] or 1,2,5-chalcogenadiazole rings [11b,23] ) and for alkyl and alkylsulfanyl substituted maleodinitriles. [24,25] It was reported that alkyl or aryl substituted fumarodinitriles having trans-configuration are inactive in cyclotrimerization with formation of subporphyrazines. [25] Since diaryl substituted maleodinitriles were not availalable, hexaarylated subporphyrazines were obtained [14] only by peripheral arylation of ethylsulfanyl substituted subporphyrazines using Pd-catalyzed Cu-mediated crosscoupling reaction with arylboronic acids with overall yield from di(ethylsulfanyl)maleonitrile not exceeding 6 %.…”

“…[24,25] It was reported that alkyl or aryl substituted fumarodinitriles having trans-configuration are inactive in cyclotrimerization with formation of subporphyrazines. [25] Since diaryl substituted maleodinitriles were not availalable, hexaarylated subporphyrazines were obtained [14] only by peripheral arylation of ethylsulfanyl substituted subporphyrazines using Pd-catalyzed Cu-mediated crosscoupling reaction with arylboronic acids with overall yield from di(ethylsulfanyl)maleonitrile not exceeding 6 %. We have observed that reaction of cis/trans-1 mixture with BCl 3 in p-xylene under reflux leads to cyclotrimerization product -perfluorophenyl substituted subporphyrazine 2, which was isolated with ca.…”

Electronic structures of azulene-fused porphyrins as seen by magnetic circular dichroism and TD-DFT calculations

“…It should be noted that the MCD spectra of cone-shaped subporphyrin [11], subphthalocyanine and subnaphthalocyanine [12] compounds also contain similar B term envelopes at slightly higher energy than the Q00 band. Although the possibility that this arises from a z-polarized transition has not been pointed out previously, the intense positive B term intensity in this region may be an indication of the presence of a z-polarized transition [11][12][13][14][15][16].…”