Synthesis and EPR studies of porphyrazines with bulky substituents

Novel porphyrazines containing peripherally functionalized macrocyclic (N2O2, N2S2) units: Synthesis and characterization

“…A second intense and broad p / p * transition in the range 300-365 nm which is called Soret or B band is also a characteristic of these tetrapyrrole derivatives (Fig. 1) [41][42][43]. In addition, heteroatom-substituted porphyrazines display intense coupling between the nonbonding, lone pair electrons and the macrocyclic p-system.…”

Synthesis and EPR studies of soluble vanadyl octakis(4-tert-butylbenzylthio) porphyrazine

“…The 1,2-bis-(4-t-butylbenzylthio)maleonitrile (TBBTMNT), octakis(4-tert-butylbenzylthio) porphyrazinato magnesium(II) (MgPz), and metal-free octakis(4-tert-butylbenzylthio) 21 H, 23 H porphyrazine (H 2 Pz) were prepared according to previously reported procedures with minor changes and characterized by comparing their spectral data to those reported earlier [13]. Mg(II) complex and metal-free porphyrazine were stable at room temperature and they were non-hygroscopic and insoluble in water but soluble in many common organic solvents.…”

“…The starting point of this new VOPz structure with eight (4-tert-butylbenzylthio) groups bound to the periphery is 1,2-bis-(4-t-butylbenzylthio)maleonitrile (TBBTMnt), which was synthesized as a solid product in relatively high yield according to the previously reported procedure (scheme 1) [13]. The presence of electron-donating sulfur is expected to shift the absorption range of the porphyrazine Q-band to higher wavelength and tert-butyl groups to enhance solubility [6,12,13,34].…”

“…Strong correlation between the nature of the substituent and the presence of soft S-donors in affecting solid-state interactions of the macrocyclic ring system, coupled with relative ease of synthesis, has led to a large series of derivatives with physical and chemical properties of the porphyrazines comparable to those of phthalocyanines [4,5]. In comparison to other family members, porphyrazines maintain a unique class due to much increased solubility in organic solvents compared with their phthalocyanine analogs and interactions with alkali or transition metal ions incorporated into the macrocycle core provides candidates for a series of applications [6][7][8][9][10][11][12][13]. Although porphyrazines possess numerous potential applications in technology including chemical sensors, molecular electronics, organic solar cells, photodynamic therapy, organic field effect transistors, biological agents, and metal-insulator-semiconductor-based devices, the electronic and paramagnetic properties of porphyrazine have not been widely studied [14][15][16][17][18][19].…”

Synthesis, structural and spectral properties of novel octakis(3,5-bis-trifluoromethyl-benzylthio) substituted porphyrazine derivatives

“…Among these, phthalocyanines with fused to or attached through bridges to macrocyclic structures and porphyrazines with long chains or functional groups such as quaternizable amino groups [18], crown ethers [19], ferrocenes [20], triphenylphosphine [21], 4-tert-buthylphenylthio [22] and tosylaminoethylthio [23] can be cited. Moreover, we have synthesized novel seco-porphyrazines substituted with (1-naphthyl) [24], (4-biphenyl) groups [25] on the peripheral positions as encountered by Barrett and co-workers, with peripheral amino derivatives [26].…”