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The role of O2 within the synthesis of phthalocyanines (Pcs) has remained unclear in the past century. Here, we demonstrate that O2, in cooperation with the solvent n-pentanol, participates in the cyclic tetramerization of phthalonitriles over the half-sandwich complex template [Lu(Pc)(acac)] (acac=acetylacetonate) and terminates the reaction at the stage of uncyclized isoindole oligomeric derivatives rather than the phthalocyanine chromophores, resulting in the isolation of the heteroleptic (phthalocyaninato)(triisoindole-1-one) lutetium double-decker complexes [(Pc)Lu(TIO-I)] (TIO-I=3,4,7,8,11,12-sexi(2,6-diisopropylphenoxy)-15-[4,5-di(2,6-diisopropylphenoxy)-2-cyanobenzimidamido]triisoindole-1-one) and [(Pc)Lu(TIO-II)] (TIO-II=3,4,7,8,11,12-sexi(2,6-dimethylphenoxy)-15-[4,5-di(2,6-dimethylphenoxy)-2-cyanobenzimidamido]triisoindole-1-one) with the help of bulky substituents at the phthalonitrile periphery and an unsubstituted phthalocyanine ligand in the double-decker skeleton. Nevertheless, the cyclic tetramerization of the phthalonitriles was revealed to be sensitive to O2 with the reaction progression also depending on the oxygen concentration/content, leading to the O2-senstive and -dependent nature for the isolation of phthalocyanine derivatives. [ABSTRACT FROM AUTHOR]

The mixed cyclic tetramerization of 4,5-bis(hexylthio)phthalonitrile and bis(diiminoisoindoline) with [M(acac)3] · nH2O (M = Pr, Eu, Lu) as template in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol at reflux has provided binuclear phthalocyanine-containing sandwich-type rare-earth complexes [{Pc(SC6H13)8}M{BiPc(SC6H13)12}M(SC6H13)8] (M = Pr, Eu, Lu; 1- 3). These new binuclear phthalocyanine-containing sandwich compounds have been characterized by a series of spectroscopic methods including mass spectrometry and 1H NMR, electronic absorption, and IR spectroscopy in addition to elemental analysis. Their electrochemical data have also been obtained by cyclic voltammetry. In addition, the third-order nonlinear optical properties of [{Pc(SC6H13)8}Pr{BiPc(SC6H13)12}Pr(SC6H13)8] ( 1) and [Pr{Pc(SC6H13)8}2] in toluene solution were studied comparatively by using the Z-scan technique; effective imaginary third-order molecular hyperpolarizabilities of 1.86 × 10-11 and 1.56 × 10-11 esu, respectively, were obtained, which indicates their potential application in the optical-limiting field. [ABSTRACT FROM AUTHOR]

Mini‐magnets: Sandwich‐type rare earth complexes involving two fused bis(phthalocyaninato) dysprosium(III) units (see figure), represent the first example of biradical–metal single molecule magnets (SMMs). These materials were synthesized and structurally characterized. Comparative investigation reveals the effective suppression of quantum tunneling of magnetization (QTM) by the π‐bridged biradical‐based antiferromagnetic interaction in the di‐dysprosium‐ion‐based SMM. [ABSTRACT FROM AUTHOR]

Developing high connectivity (>8) three‐dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine‐based (Pc‐based) 3D COFs MPc‐THHI‐COFs (M=H2, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24‐octacarboxyphthalocyanine M(TAPc) (M=H2, Ni) and 5,5′,5′′,5′′′,5′′′′,5′′′′′‐(triphenylene‐2,3,6,7,10,11‐hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X‐ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non‐interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc‐THHI‐COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for H2O2 generation from O2 and H2O via 2e− oxygen reduction reaction and 2e− water oxidation reaction under visible‐light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials. [ABSTRACT FROM AUTHOR]

Developing high connectivity (>8) three‐dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine‐based (Pc‐based) 3D COFs MPc‐THHI‐COFs (M=H2, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24‐octacarboxyphthalocyanine M(TAPc) (M=H2, Ni) and 5,5′,5′′,5′′′,5′′′′,5′′′′′‐(triphenylene‐2,3,6,7,10,11‐hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X‐ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non‐interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc‐THHI‐COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for H2O2 generation from O2 and H2O via 2e− oxygen reduction reaction and 2e− water oxidation reaction under visible‐light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials. [ABSTRACT FROM AUTHOR]

The post-cyclization strategy rather than the conventional ante-cyclotetramerization method was employed for the synthesis of multinuclear phthalocyanine-fused molecular nanoarrays. Reaction of 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-23,24-diaminophthalocyaninato zinc(II) with 2,7-di- tert-butylpyrene-4,5-dione, 2,7-di- tert-butylpyrene-4,5,9,10-tetraone, and hexaketocyclohexane in refluxing acetic acid afforded the corresponding mono-, bi-, and trinuclear phthalocyanine-fused zinc complexes (Pz-pyrene){Zn[Pc(OC8H9)6]} ( 1), (Pz2-pyrene){Zn[Pc(OC8H9)6]}2 ( 2), {(HAT){Zn[Pc(OC8H9)6]}3} ( 3) in 46, 13, and 25 % yield, respectively, which extend the scope of multinuclear phthalocyanine-fused nanoarrays with different molecular skeletons. The self-assembly behavior of trinuclear phthalocyanine 3 in THF/CH3CN was investigated by electronic absorption spectroscopy and SEM, and the fabricated nanorods showed interesting semiconducting properties, which suggest good application potential of these multinuclear phthalocyanine-fused molecular nanoarrays. [ABSTRACT FROM AUTHOR]

Phthalocyanine (Pc) and porphyrin (Por) chromophores have been fused through the benzo[ α]pyrazine moiety, resulting in unprecedented heteroleptic tetrapyrrole-fused dimers and trimers. The heteroleptic tetrapyrrole nature has been clearly revealed based on single-crystal X-ray diffraction analysis of the zinc dimer. Electrochemical analysis, theoretical calculations, and time-resolved spectroscopic results disclose that the two/three-tetrapyrrole-fused skeletons behave as one totally π-conjugated system as a result of the strong conjugative interaction between/among the tetrapyrrole chromophores. In particular, the effectively extended π-electron system through the fused-bridge induced strong electronic communication between the Pc and Por moieties and large transition dipole moments in the Pc-Por-fused systems, providing high fluorescence quantum yields (>0.13) and relatively long excited state lifetimes (>1.3 ns) in comparison with their homo-tetrapyrrole-fused analogues. [ABSTRACT FROM AUTHOR]

Novel pyrene-fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-22,25-diaza(2,7-di- tert-butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz-pyrene)(OC8H9)6] ( 1) and 2,3,9,10-tra(2,6-dimethylphenoxy)-15,18,22,25-traza(2,7-di- tert-butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz-pyrene)2(OC8H9)4] ( 2) were isolated for the first time. These unsymmetrical pyrene-fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene-fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X-ray diffraction analysis of 1, representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene. [ABSTRACT FROM AUTHOR]

Unsymmetrical Pyrene ‐ Fused Phthalocyanine In the Communication on page 3168 ff., J. Jiang et al. present novel pyrene ‐ fused unsymmetrical phthalocyanine derivatives, which were isolated and characterized by a wide range of spectroscopic and electrochemical methods for the first time. In particular, the pyrene ‐ fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X ‐ ray diffraction analysis of the monopyrene ‐ fused phthalocyaninato zinc derivative, representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene. [ABSTRACT FROM AUTHOR]