Photoactive preorganized subphthalocyanine-based molecular tweezers for selective complexation of fullerenes

Abstract

A tweezer-like subphthalocyanine-based ensemble has been developed for the selective recognition of fullerenes. The physicochemical properties of both the photoactive receptor and its inclusion complexes with fullerenes have been investigated.

Subphthalocyanine capsules: molecular reactors for photoredox transformations of fullerenes

“… 10 Electron-acceptor fullerenes are by far the most widely used units merged with SubPcs, particularly in a supramolecular manner, due to the shape complementarity between the concave face of SubPcs and the spherical π-surface of the fullerenes. 11 An outstanding illustration of this type of interaction is that exhibited by the SubPc-based coordination cage 2 reported by our group ( Fig. 1 ), formed by Pd-directed dimerization of two C 3 -symmetry SubPcs 1 endowed with three peripheral 3-pyridyl units, 12 which form stable 1 : 1 host–guest complexes with C 60 and C 70 .…”

Recent advances in subphthalocyanines and related subporphyrinoids

“…During the last years, the synthesis of several unsymmetrical SubPc derivatives has been reported, including the preparation of low-symmetry SubPcs bearing peripheral ortho -substituents. 14,17,47–58…”

“…Axial substitution of the axial chlorine atom with phenols is commonly carried out by refluxing the starting SubPc-Cl with the corresponding alcohol in a high-boiling point aromatic solvent such as toluene, 46–48,50,53–56,58,70,73,76,91–117 1 : 1 toluene/THF mixture, 118 chlorobenzene, 17,119 dichlorobenzene (DCB) 29,30 and o -xylene. 120 Interestingly, reaction of SubPc-Cl, SubPc-Br and mesylated SubPcs with phenols in DMF was found to afford the corresponding formate derivative in addition to the target phenoxy conjugate and the hydrolyzed SubPc-OH product ( vide infra ).…”

“…1 Here, the publications dealing with SubPc peripheral reactivity which are subsequent to our previous review on contracted poprhyrinoids 1 are summarized. 11 Sonogashira coupling reactions of peripherally iodo-substituted SubPc precursors in the presence of ethynyl-pyridine, 92 propargylic acid, 47 ethynyl-benzoic acid, 47,50 4-(7-ethynyl-2,1,3-benzothiadiazol-4-yl) ethynyl-benzoic acid, 55 tris(dodecyloxy)phenylacetylene, 102 ethynyl-thiophene derivatives, 171 ethynyltrimethylsilane and (triisopropylsilyl)acetylene, 75 a tetraethynylethene derivative, 53 1,2-diethynyl benzene, 172 ethynyl- N , N -dimethylaniline, 46,55 trimethylsilyl-protected ethynylferrocene and butadyineferrocene, 56 ethynyl perylenediimide precursors, 173 ethynylated dihydroazulene, 57 and a bis(ethynyl)boron-functionalized SubPc dimer 58 have been reported, as well as the coupling between 1,4-diethynyl benzene and the peripherally bromo-substituted SubPc precursors. 169 Suzuki reactions of pyreneboronic acid and phenylboronic acid tethered pyrene with iodophenoxy-SubPcs, 164 of ferroceneboronic acid 111 and aminophenylboronic acid pinacol ester 174 with iodo-SubPcs, of thiophene boronic acid pinacol ester derivatives with bromo-SubPcs, 116 and of bromo terpyridine with borylated SubPc species 15 have also been published.…”

Photoresponsive polymers with dangling triptycene units as efficient receptor for fullerene‐C60

“…2 This has in turn inspired a surge of research interest for the development of various host molecules, which bind efficiently with fullerene. [11][12][13][14][15][16] Additionally, the development of artificial receptors (molecular sensor and tweezers) is one of the most interesting topics of research in supramolecular chemistry. 5,12 On the other hand, triptycene has a rigid 3D structure in which three electron rich phenyl rings are oriented in a paddle wheel fashion with concave shaped cavities (Chart 1).…”