Phthalocyanines bearing bulky cycloalkylmethyl substituents on non-peripheral sites

1,4,8,11,15,18,22,25-Alkylsulfanyl phthalocyanines: effect of macrocycle distortion on spectroscopic and packing properties

“…The dihedral angles between the four isoindole rings and the mean plane formed by the four pyrrole nitrogens that goes through N 4 (isoindole) atoms (N8, N12, N16 and N20) are 3.411, 5.591, 4.721, 9.641, respectively. The ring planarity is similar to that of previously published nonperipherally octasubstituted phthalocyanines (Table S2, ESI, † entries 2, 9 4, 10 5 11 and 7 12 ). 2 crystallizes in the non-centrosymmetric cubic space group P% 43n.…”

Tuning the Structure and Photophysics of a Fluorous Phthalocyanine Platform

“…Substitution of the β positions is kinetically favored, and thus the first eight substitutions do not greatly alter the structure of the planar macrocycle. Upon substitution of the remaining α positions, however, steric interactions begin to either lower the energy barrier to nonplanar vibrations or force nonplanar distortions ( vide infra ). − ,− …”

“…Disrupting the normally planar aromatic system induces drastic changes in the photophysics, with important consequences for potential applications. To date, syntheses of structurally distorted Pcs have only been accomplished through the cyclotetramerization of phthalonitriles or similar precursors already bearing bulky groups in the α position, − thereby limiting the scope of this approach. In this context, exploiting the synthetic versatility of the ZnF 16 Pc platform is an important part of the rapid design and testing of Pc compounds for commercially viable applications.…”

Negishi coupling in the synthesis of advanced electronic, optical, electrochemical, and magnetic materials

“…With Negishi coupling, a series of precursors 145 for the synthesis of phthalocyanines 146 can be prepared from the bis-triflate derivative 144. [115][116][117] The inexpensive NiCl 2 (PPh 3 ) 2 was used as an effective catalyst for this transformation. Suzuki coupling with the in situ generated tridecylborane to introduce the alkyl group was reported to give the desired product in much lower yields (∼30%) under various conditions including using PdCl 2 (dppf ) as the catalyst and K 3 PO 4 or K 2 CO 3 as the bases (Scheme 37).…”

“…With Negishi coupling, a series of precursors 145 for the synthesis of phthalocyanines 146 can be prepared from the bis-triflate derivative 144 [115][116][117]. Phthalocyanines, structurally similar to porphyrins, are another family of optically important compounds having found applications in solar cells, photodynamic therapy, optical data storage and being used as nonlinear optical and optical limiting materials.…”