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71.
    
A comparative investigation of the chiral amplification features of a series of three families of C3-symmetric tricarboxamides, 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs), is here reported. As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE-TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures.  相似文献   
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The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C60 dyads has been investigated. For this, two C60-SiPc-C60 dyads, 1 and 2 , varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C60-SiPc-C60 1 where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with kcs equal to 2.7×109 s−1 in benzonitrile. However, in the case of C60-SiPc-C60 2 , where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, kcs=9.1×108 s−1, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc.+-C60.− charge separated states (1.57 eV) populated the low-lying 3SiPc* (1.26 eV) prior returning to the ground state.  相似文献   
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The reactivity of 3-methyl-5-phenylisoxazole against electrophilic compounds in the presence of different bases is studied. With n-BuLi, alkylated products at C-4 position and C-3 methyl group, and, in a few cases, dialkylated isoxazoles are obtained. When the reactions are carried out with LICA, the nature of the alkylated products depends on the alkyl halide used. By using LICA-TMEDA, as deprotonating system, regio-selective reaction at the C-3 methyl group is found.  相似文献   
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On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV.  相似文献   
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Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr3 perovskite NC colloids into large area (1 cm2) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.  相似文献   
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The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B3H4+ analogues.  相似文献   
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