Abstract:Two related nickel(II) porphyrins,
etioporphyrin-I (Etio-I) and
octaethylporphyrin (OEP), were cocrystallized with C70 to
produce the new cocrystal structures C70·Ni(Etio-I)·2C6H6 and C70·Ni(OEP)·2C6H6. Etio-I is a variant of OEP, where four alternating
ethyl groups from OEP are replaced with methyl substituents. This
isomer of etioporphyrin has the potential to act as an agent in chiral
sorting of asymmetric fullerenes. However, the replacement of four
ethyl groups has nontrivial structural consequences.… Show more
“…The notation 2DPC{C 60 } is adopted to specify this unique supramolecular (+)hand-ball-hand(−) assembly in which the buckyball C 60 is cradled by both chiral DPC hosts. Based on the interesting concept reported in Balch’s article 34 , our DPC hosts provides a valuable opportunity to sort chiral fullerene enantiomers in the future. Fig.…”
Section: Resultsmentioning
confidence: 99%
“…Although the goal of sorting chiral fullerene enantiomers was not achieved in the example of 2DPC{α-PC 71 BM}, it is worth trying more experiments in the future. Sorting chiral fullerene enantiomers might be possible since DPC can become chiral upon crystallization though it is intrinsically achiral in solution, as mentioned in Balch’s article 34 . This important characteristic provides valuable opportunities and new thoughts for sorting fullerene enantiomers by DPC.…”
The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement. Here we show a chiral configuration of decapyrrylcorannulene that has a concave ‘palm’ of corannulene and ten flexible electron-rich pyrryl group ‘fingers’ to mimic the smart molecular ‘hands’ for self-adaptably cradling various buckyballs in a (+)hand-ball-hand(−) mode. As exemplified by crystallographic identification of 15 buckyball structures representing pristine, exohedral, endohedral, dimeric and hetero-derivatization, the pyrryl groups twist with varying dihedral angles to adjust the interaction between decapyrrylcorannulene and fullerene. The self-adaptable electron-rich pyrryl groups, susceptible to methylation, are theoretically revealed to contribute more than the bowl-shaped palm of the corannulene in holding buckyball structures. The generality of the present decapyrrylcorannulene host with flexible pyrryl groups facilitates the visualization of numerous unknown/unsolved fullerenes by crystallography and the assembly of the otherwise close-packed spherical fullerenes into two-dimensional layered structures by intercalation.
“…The notation 2DPC{C 60 } is adopted to specify this unique supramolecular (+)hand-ball-hand(−) assembly in which the buckyball C 60 is cradled by both chiral DPC hosts. Based on the interesting concept reported in Balch’s article 34 , our DPC hosts provides a valuable opportunity to sort chiral fullerene enantiomers in the future. Fig.…”
Section: Resultsmentioning
confidence: 99%
“…Although the goal of sorting chiral fullerene enantiomers was not achieved in the example of 2DPC{α-PC 71 BM}, it is worth trying more experiments in the future. Sorting chiral fullerene enantiomers might be possible since DPC can become chiral upon crystallization though it is intrinsically achiral in solution, as mentioned in Balch’s article 34 . This important characteristic provides valuable opportunities and new thoughts for sorting fullerene enantiomers by DPC.…”
The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement. Here we show a chiral configuration of decapyrrylcorannulene that has a concave ‘palm’ of corannulene and ten flexible electron-rich pyrryl group ‘fingers’ to mimic the smart molecular ‘hands’ for self-adaptably cradling various buckyballs in a (+)hand-ball-hand(−) mode. As exemplified by crystallographic identification of 15 buckyball structures representing pristine, exohedral, endohedral, dimeric and hetero-derivatization, the pyrryl groups twist with varying dihedral angles to adjust the interaction between decapyrrylcorannulene and fullerene. The self-adaptable electron-rich pyrryl groups, susceptible to methylation, are theoretically revealed to contribute more than the bowl-shaped palm of the corannulene in holding buckyball structures. The generality of the present decapyrrylcorannulene host with flexible pyrryl groups facilitates the visualization of numerous unknown/unsolved fullerenes by crystallography and the assembly of the otherwise close-packed spherical fullerenes into two-dimensional layered structures by intercalation.
“…Scheme 1 shows the structure of Ni-(Etioporphyin-I). Our numerous attempts to grow cocrystals of C 60 with Ni(Etioporphyin-I) failed, 39 but slow crystal growth yielded the new benzene solvate in the form of black blocks. This new solvate crystallizes in the monoclinic space group P2 1 /n.…”
Section: The Journal Of Physical Chemistry Amentioning
The solid-state structures of seven solvates of C 60 (C 60 •4tetrachloroethylene, C 60 •2tetrachloroethylene, C 60 • 3benzene, C 60 •n-pentane, C 60 •diethyl ether, C 60 •chlorobenzene, and C 60 •benzene•dichloromethane) were determined by single-crystal X-ray diffraction at low temperature. At 90 K, the fullerene and solvate components are generally wellordered and do not show the orientational disorder that plagues similar structures determined at room temperature. Interactions between the solvate molecules and the fullerene and between adjacent C 60 molecules were examined and analyzed. Van der Waals and weak charge-transfer interactions are important to help to organize the individual components in these structures. The weak Lewis acid behavior of C 60 , such as when it cocrystallizes with diethyl ether or chlorinated solvents, is apparent. In addition, π-stacking interactions are prevalent. The solvates of C 60 reported here were frequently obtained from attempts to cocrystallize C 60 with another chemical compound. Although the desired cocrystals were never formed, the unincorporated molecules influenced solvate formation.
“…halide for halide, increasing sizes of alkyl groups, etc. [41][42][43][44][45][46][47][48][49][50][51][52][53] are evaluated. Usually some systematic trends can be discerned suggesting remote substituents are non-innocent, providing specific points of contact between molecules but, not always.…”
X-ray crystallography reveals the common feature of the title compounds is a 1,4-naphthoquinone ring system with a substituted phenoxy residue adjacent to an oxo-group to give 1 (H), 2 (3-Br), 3 (3-CF3), 4 (4-CN) and 5 (4-NO2). To a first approximation the fused ring system along with the two oxo substituents is planar with the major difference between the molecules relating to the relative orientations of the pendant phenoxy residues: dihedral angles range from 56.56(4)° (3) to 87.52(10)° (2). The presence of intermolecular C–H···O interactions is the common feature of the supramolecular association in the crystals of 1–5. In each of 1 and 5, these extend in three-dimensions but, only to supramolecular dimers in 4, chains in 2 and layers in 3. Each crystal also features C=O···π interactions, pointing to the importance of these points of contact in this series di-oxocompounds. In 2, these, along with C–Br···π interactions lead to a three-dimensional architecture. For 3, the C=O···π and π···π interactions occur within the layers which stack without directional interactions between them. In 4, C–H···O and C=O···π interactions combine to give a supramolecular layer, which also stack without directional interactions in the inter-layer region. Further analysis of the molecular packing was conducted by a Hirshfeld surface analysis (HSA). This points to the significant role of H···H, C···H/H···C and O···H/H···O contacts in the packing of 1. Notably different roles for these contacts are found in the other crystals correlating with the participation of the respective substituents in the molecular packing. The HSA suggests the association between layers in 3 (weak F···F and H···F interactions) and 4 (weak H···N interactions) is contributed by the phenoxy-substituents.
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