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It should be noted that the NDI dibromide used for clipping reaction is mixed with impurities resulted from decomposition under the acidic bromination conditions and cannot be purified due to limited solubility. These impurities, together with the poorer solubility of NDI dibromide 2, are probably responsible for lower yields than the corresponding PMI derivatives
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It should be noted that the NDI dibromide used for clipping reaction is mixed with impurities resulted from decomposition under the acidic bromination conditions and cannot be purified due to limited solubility. These impurities, together with the poorer solubility of NDI dibromide 2, are probably responsible for lower yields than the corresponding PMI derivatives.
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Crystals suitable for X-ray single crystal analysis were obtained after diffusion of ether into a Me2CO solution or from a MeCN solution after diffusion of diisopropyl ether. For more crystallographic information, see the crystallographic information files in Supporting Information
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2CO solution or from a MeCN solution after diffusion of diisopropyl ether. For more crystallographic information, see the crystallographic information files in Supporting Information.
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Two mechanisms are possible for the exchange between the two translational isomers. Either the dicationic cyclophane rotates through the center of the crown ether component, or the outer DNP unit can sweep round the dicationic cyclophane by pirouetting about the included DNP moiety. According to studies by the Stoddart group on structurally similar [2]catenanes, see: Stoddart, J. F; et al. J. Am. Chem. Soc. 1992, 114, 193-218., the latter one is the lower energy process as it requires least energy for the breakdown of donor-acceptor interactions. The typical associated activation barrier for Stoddart's systems is around 12-14 kcal mol-1. Correspondingly, those site exchange processes can be efficiently frozen out below 243 K. For compounds 6•2PF6 and 7•2PF6, such activation barrier is difficult to measure on account of the absence of other isomers. However, they should be very similar to those r
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2+ and the outer aromatic units.
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See Supporting Information
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See Supporting Information.
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It can be noticed that the TTF-BPY2+ CT band of catenanes 82+ and 112+ has almost the same molar absorption coefficient as that of model compound 174, although the former catenanes possess only one BPY2+ unit. Indeed, it was recently shown (ref 4g) that the alongside CT interaction between a TTF and a BPY2+ units can give rise to a band with an absorption coefficient similar to that of the present catenanes. As observed in previous investigations on related catenanes refs 15c, g, the CT band intensities in this type of catenanes do not usually scale linearly with the number of donor and acceptor units involved
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2+ units can give rise to a band with an absorption coefficient similar to that of the present catenanes. As observed in previous investigations on related catenanes (refs 15c, g), the CT band intensities in this type of catenanes do not usually scale linearly with the number of donor and acceptor units involved.
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A very weak HQ- or DNP-type fluorescence, whose intensity was from two to three orders of magnitude smaller than that of the crown ethers 3 or 4, respectively, was detected upon UV excitation. Fluorescence lifetime measurements indicate that such emissions originate from small amounts of strongly emissive impurities.
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A very weak HQ- or DNP-type fluorescence, whose intensity was from two to three orders of magnitude smaller than that of the crown ethers 3 or 4, respectively, was detected upon UV excitation. Fluorescence lifetime measurements indicate that such emissions originate from small amounts of strongly emissive impurities.
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