The cycloparaphenylenes (CPPs) are a class of strained macrocycles that until 2008 were considered beyond the reach of organic synthesis. With its cyclic array of ten para-substituted phenylene rings, [10]CPP possesses a concave π-system that is perfectly preorganized for the strong supramolecular association of convex fullerenes such as C60. Although mechanically interlocked CPP architectures have been observed in the gas phase, the rational synthesis of bulk quantities has not been achieved yet, which is likely due to the fact that conventional template strategies are not amenable to CPP rings that lack heteroatoms. Here, we report the synthesis of two [2]rotaxanes in which a [10]CPP ring binds to a central fullerene bis-adduct and is prevented from dethreading by the presence of two bulky fullerene hexakis-adduct stoppers. The final step in the rotaxane synthesis is surprisingly efficient (up to ca. 40% yield) and regioselective because the fullerene acts as an efficient convex template, while [10]CPP acts as a supramolecular directing group, steering the reaction at the central fullerene exclusively toward two trans regioisomers. Comprehensive physicochemical studies confirmed the interlocked structure, shed light on the dynamic nature of the CPP–fullerene interaction, and revealed intriguing consequences of the mechanical bond on charge transfer processes. In light of recent advances in the synthesis of nanohoops and nanobelts, our concave–convex π–π templating strategy may be broadly useful and enable applications in molecular electronics or complex molecular machinery.
Efficient photoinduced electron transfer was observed across a [10]cycloparaphenylene ([10]CPP) moiety that serves as a rigid non-covalent bridge between a zinc porphyrin and a range of fullerenes. The preparation of iodo-[10]CPP is the key to the synthesis of a porphyrin-[10]CPP conjugate, which binds C , C , (C ) , and other fullerenes (K >10 m ). Fluorescence and pump-probe spectroscopy revealed intramolecular energy transfer between CPP and porphyrin and also efficient charge separation between porphyrin and fullerenes, affording up to 0.5 μs lifetime charge-separated states. The advantage of this approach towards electron donor-acceptor dyads is evident in the case of dumbbell-shaped (C ) , which gave intricate charge-transfer behavior in 1:1 and 2:1 complexes. These results suggest that [10]CPP and its cross-coupled derivatives could act as supramolecular mediators of charge transport in organic electronic devices.
Graphene-porphyrin nanohybrid materials with a direct covalent linkage between the graphene carbon network and the functional porphyrin unit have been successfully synthesized via a one-pot reductive diazotation approach. A graphite-potassium intercalation compound (KC) was dispersed in THF, and different isolated porphyrin-diazonium salts were added. The direct covalent binding and the detailed characterization of the functional hybrid material were carried out by Raman spectroscopy, TG-MS, UV/vis, and fluorescence spectroscopy. LDI-ToF mass spectrometry was introduced as a new versatile and sensitive tool to investigate covalently functionalized graphene derivatives and to establish the composition of the respective nanohybrid materials.
Small π-conjugated nanohoops are difficult to prepare, but offer an excellent platform for studying the interplay between strain and optoelectronic properties and increasingly, these shape-persistent macrocycles find uses in host-guest chemistry and self-assembly. We report the synthesis of a new family of radially π-conjugated porphyrinylene/phenylene nanohoops. The strain energy in the smallest nanohoop [2]CPT is approximately 54 kcal mol -1 , which results in a narrowed HOMO-LUMO gap and a red shift in the visible part of the absorption spectrum. Due to its high degree of preorganization and a diameter of ca. 13 Å, [2]CPT was found to accommodate C60 with a binding affinity exceeding 10 8 M -1 despite the fullerene not fully entering the cavity of the host (X-Ray crystallography). Moreover, the π-extended nanohoops [2]CPTN , [3]CPTN and [3]CPTA (N for 1,4-naphthyl; A for 9,10anthracenyl) have been prepared using the same strategy, and [2]CPTN has been shown to bind C70 five times more strongly than [2]CPT. Our failed synthesis of [2]CPTA highlights a limitation of the experimental approach most commonly used to prepare strained nanohoops, because in this particular case the sum of aromatization energies no longer outweighs the buildup of ring strain in the final reaction step (DFT calculations). These results indicate that forcing ring strain onto organic semiconductors is a viable strategy to fundamentally influence both optoelectronic and supramolecular properties.
[ n ]Cycloparaphenylenes ([ n ]CPPs) with n =5, 8, 10 and 12 and their noncovalent ring‐in‐ring and [ m ]fullerene‐in‐ring complexes with m =60, 70 and 84 have been studied by direct and matrix‐assisted laser desorption ionization ((MA)LDI) and density‐functional theory (DFT). LDI is introduced as a straightforward approach for the sensitive analysis of CPPs, free from unwanted decomposition and without the need of a matrix. The ring‐in‐ring system of [[10]CPP⊃[5]CPP] +. was studied in positive‐ion MALDI. Fragmentation and DFT indicate that the positive charge is exclusively located on the inner ring, while in [[10]CPP⊃C 60 ] +. it is located solely on the outer nanohoop. Positive‐ion MALDI is introduced as a new sensitive method for analysis of CPP⊃fullerene complexes, enabling the detection of novel complexes [[12]CPP⊃C 60, 70 and 84 ] +. and [[10]CPP⊃C 84 ] +. . Selective binding can be observed when mixing one fullerene with two CPPs or vice versa, reflecting ideal size requirements for efficient complex formation. Geometries, binding and fragmentation energies of CPP⊃fullerene complexes from DFT calculations explain the observed fragmentation behavior.
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