Although many noble-metal catalysts have been used for the oxidation of organosilanes, there has been less success with non-noble-metal catalysts. Here, unsupported nanoporous copper (np-Cu) is used to catalyze the oxidation of organosilanes under mild conditions. It is the first time that this reaction has been achieved with a heterogeneous copper catalyst with high activity and selectivity. Both water and alcohols are used as oxidants and the corresponding organosilanols and organosilyl ethers are obtained in high yield. The possible mechanism was obtained by kinetic studies. The catalyst could be reused at least five times without evident loss of activity. As a novel green catalyst np-Cu should play a unique role in organic synthesis.

Three phthalocyanine derivatives with four peripheral chiral (S)-2-methylbutoxy moieties at the α or β positions of the phthalocyanine ring have been synthesized. The CD spectra of compounds 1 and 2, each containing four peripheral chiral (S)-2-methylbutoxy moieties at the α positions of the phthalocyanine ring, show CD signals in the Q-absorption region of the phthalocyanine chromophores. However, no CD signal was observed in the whole absorption region for compound 3, which contains four peripheral chiral (S)-2-methylbutoxy moieties at the β positions of the phthalocyanine ring. These results indicate the influence of the position of the chiral substituents on the chiral transfer and expression at a molecular level. Further investigation of the self-assembly behavior of compounds 1 and 2 revealed that the metal-free phthalocyanine 1 self-assembles into a nanocube whereas its zinc congener, [(S)-ZnPc(α-OC₅H₁₁)₄] (2), self-assembles into helical nanobelts, which implies an effect of metal coordination on the morphology and handedness of the self-assembled nanostructures.

Two optically active phthalocyanine derivatives with eight peripheral chiral (S)-4′-(2-methylbutoxy)biphenyl moieties on the β-position of the phthalocyanine ring are synthesized. The circular dichroism (CD) spectra show signals in the Q absorption region for both compounds 1 and 2 in chloroform solution, indicating the effective chiral-information transfer from the peripheral chiral (S)-4′-(2-methylbutoxy)biphenyl side chains to the phthalocyanine chromophore at the molecular level. Their self-assembling properties are further investigated by using electronic absorption and Fourier transform infrared spectroscopy, transmission electronic microscopy, scanning electronic microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Experimental results reveal the effect of the metal-coordination bond on molecular packing models in these nanostructures, which in turn results in the self-assembled nanostructures with different morphologies, from nanosheets for 1 to helical nanofibers for 2. In addition, good semiconducting properties of the nanostructures fabricated from phthalocyanine derivatives 1 and 2 are revealed by current–voltage measurements.

To investigate the effect of sulfur–sulfur and metal–ligand coordination on the molecular structure and morphology of self-assembled nanostructures, metal-free 2,3,9,10,16,17,23,24-octakis(isopropylthio)phthalocyanine H₂Pc(β-SC₃H₇)₈ (1) and its copper and lead congeners CuPc(β-SC₃H₇)₈ (2) and PbPc(β-SC₃H₇)₈ (3) are synthesized and fabricated into organic nanostructures by a phase-transfer method. The self-assembly properties are investigated by electronic absorption and Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Experimental results reveal different molecular packing modes in these aggregates, which in turn result in self-assembled nanostructures with different morphologies ranging from nanobelts for 1 through nanoribbons for 2 to cluster nanoflowers for 3. Intermolecular π–π and sulfur–sulfur interactions between metal-free phthalocyanine 1 lead to the formation of nanobelts. The additional CuS coordination bond between the central copper ion of 2 and the sulfur atom of the adjacent molecule of 2 in cooperation with the intermolecular π–π stacking interaction increases the intermolecular interaction, and results in the formation of long nanoribbons for 2. In contrast to compounds 1 and 2, the special molecular structure of complex 3, together with the intermolecular π–π stacking interaction and additional PbS coordination bond, induces the formation of Pb-connected pseudo-double-deckers during the self-assembly process, which in turn further self-assemble into cluster nanoflowers. In addition, good semiconducting properties of the nanostructures fabricated from phthalocyanine derivatives 1–3 were also revealed by I–V measurements.

(D)- and (L)-enantiomers of a novel metal-free 2(3),9(10),16(17),23(24)-tetrakis(2-isopropyl-5-methylcyclohexoxyl)phthalocyanine (1) with four chiral menthol units attached at the peripheral positions of a phthalocyanine ligand have been synthesized, and characterized. Neither the (D)-1 nor the (L)-1 enantiomer display a circular dichroism (CD) signal in the Soret and Q absorption region of the phthalocyanine ligand, indicating the lack of effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the molecular level. Their self-assembly properties were systematically studied by CD spectroscopy, transmission electron microscopy, scanning electron microscopy, and atom force microscopy technique. Although four constitutional stereoisomers of each enantiomer were synthesized, because the four chiral menthol substituents are randomly located at peripheral positions of the phthalocyanine ring, cooperation of intermolecular π–π interactions between the phthalocyanine rings with chiral discrimination of the chiral side chains of the (D)-1 and the (L)-1 enantiomer induces the formation of one-dimensional helices with left- and right-handed helical molecular arrangement, respectively, according to the CD spectroscopic results. This reveals the effective chiral information transfer from the chiral menthol tails to the phthalocyanine chromophore at the supermolecular level. The formed one-dimensional helices twist around each other to maximize the van der Waals interaction, leading to the formation of highly ordered fibrous nanostructures with both right- and left-handed helicity according to the staggering angles between the neighboring phthalocyanine molecules, indicating the hierarchical formation of these fibrous nanostructures. Careful inspection of these nanofibers indicates the majority of nanofibers with right- and left-handed helicity formed from (D)-1 and (L)-1 enantiomer, respectively, with the ratio of approximately 1.3–1.4:1 among all the fibrous nanostructures obtained. Electronic absorption spectroscopic and X-ray diffraction results reveal the H-aggregate nature of these nanofibers. The present results, showing part of our continuous effort towards preparation of self-assembled nanostructures with helical morphology through molecular design and synthesis, will be helpful on providing new insight into chiral information transfer and expression for synthetic conjugated systems at the supermolecular level.