Three dimensional isophlorinoid tetrapodal molecular cage

Abstract

Steric hindrance induced by thiophene molecules in predesigned precursors favors the exclusive formation of three dimensional (3D) π-conjugated cage and quasi-cage like molecules instead of porphyrinoid macrocycle. Herein we report...

Controlled assembly of a bicyclic porphyrinoid and its 3-dimensional boron difluoride arrays

“…Further support for the conformational exibility of the BODIPY arrays came from 19 F NMR spectral studies. For instance, in the 19 F NMR spectrum of 4$4BF 2 , a relatively small number of signals is seen at ambient temperature as would be expected for a system subject to conformational dynamics (Fig. S25 †).…”

“…S31-S33 †). The molecular structures of 4$2BF 2 , 4$3BF 2 , and 4$4BF 2 were established on the basis of 1 H, 19 F, and 11 B NMR spectroscopic analyses. In contrast to 4, the VT 1 H NMR spectra of all these BODIPY arrays recorded in THF-d 8 displayed features consistent with a degree of conformational exibility on the NMR time scale; however, all expected signals were visible at lower temperatures (cf.…”

“…18 However, the synthesis of three dimensional porphyrinoids skeleton remains challenging and can be hampered by poor yields resulting from metal-mediated reactions 18 or the concomitant generation of monocyclic or polymeric by-products. 17,19,20 Here we report that by condensing a carbazole-containing 2,2 0 -bipyrrole analogue 1 with a 2,5diformylpyrrole one can obtain either a monocyclic gure-eight porphyrinoid 3 in 82% yield or a bicyclic cryptand-like porphyrinoid 4 in 79% yield depending on the choice of conditions (Scheme 1). The 3D system 4, which is the focus of the present report, contains four co-planar dipyrrin units.…”

“…[13][14][15] However, fully conjugated topographically nonplanar oligopyrroles, so-called three dimensional (3D) porphyrinoids, remain rare. [16][17][18][19] For example, in 2008 Setsune and co-workers described a pyridine-containing cryptand-like bicyclic hexapyrrole with three dipyrrylpyridine linkages that demonstrated positive cooperativity in binding carboxylic acids. 20 Our own group also reported a fully conjugated 3D carbaporphyrinoid cage encompassing a dibenzo [g,p] chrysene moiety.…”

A Triply [5]Helicene‐Bridged (1,3,5)Cyclophane

“…Progress in the synthesis of three-dimensional π-conjugated macrocycles has been considerable in recent years, [1] introducing new systems for host-guest chemistry [2,3] and allowing new insights into the concept of aromaticity. [1,4] Among the many examples of 3D conjugated macrocycles [5][6][7] reported recently, conjugated hydrocarbons have been a rarity since the introduction of the nanoball by Itami [8] and Yamago. [9] Amid the newer examples, some interesting radical behavior [10] and distorted [5]helicene structures [11] have been reported (Figure 1).…”