A novel synthesized 4-carboxylphenoxy-decorated tetraphenylethene and α-cyclodextrin could form a host–guest inclusion complex with molecular RIM-induced Emission. On the basis of this, the TPE-COOH⊂α-CD inclusion complex exhibits a reversible fluorescence intensity change response to the photo-isomerization of 4-(phenylazo)benzoic acid (PBA) under alternate UV- and visible-light irradiation.

Terbium orthophosphate nanoparticles were synthesized using 1-hydroxy ethylidene-1,1-diphosphonic acid(HEDP) as a capping ligand under hydrothermal conditions at 80 °C. These HEDP-capped TbPO4 nanoparticles owned a hexagonal phase structure according to the powder X-ray diffraction(XRD) results and were spherical monodispersed particles with a diameter of about 10 nm confirmed by transimission electron microscope(TEM) images. Interestingly, the luminescent intensities of the HEDP-capped TbPO4 nanoparticles decreased obviously in the presence of Pb2+ ions and such a quenching behavior of luminescence was well fitted by the Stern-Volmer equation.

Cyclic tetramerization of 3-[(methyloxycarbonyl)phenoxy]phthalonitrile (1a–1c) in the presence of Zn(OAc)2·2H2O and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by transesterification in refluxing n-pentanol afforded 1(4),8(11),15(18),22(25)-tetrakis[(pentyloxycarbonyl)phenoxy]phthalocyaninato zinc(II) complexes (2a–2c) as a mixture of four constitutional isomers. Simple silica-gel column chromatography leads to the successful separation of pure isomers with the C4h and D2h symmetry together with a section containing the C2v and Cs isomers, which have been characterized with a wide range of spectroscopic methods including MALDI-TOF mass, electronic absorption, 1H NMR, and 2D COSY spectroscopy. Synthesis yields in combination with the NMR spectroscopic results reveal that the distribution of the four isomers in the final product for 2a–2c does not strictly follow that expected according to statistical calculation with the ratio of C4h:C2v:Cs:D2h = 1:2:4:1, indicating the effect of steric hindrance of substituents on the formation of various constitutional isomers.Graphical abstractCyclic tetramerization of 3-[(methyloxycarbonyl)phenoxy]phthalonitrile in the presence of Zn(OAc)2·2H2O and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by transesterification in refluxing n-pentanol afforded the four constitutional isomers of 1(4),8(11),15(18),22(25)-tetrakis[(pentyloxycarbonyl)phenoxy]phthalocyaninato zinc(II) complexes, which in particular the C4h and D2h isomers have been easily separated by simple silica-gel column chromatography.Highlights► A series of 1(4),8(11),15(18),22(25)-substituted phthalocyanines have been prepared. ► The C4h and D2h isomers have been separated on simple silica-gel column chromatography. ► The distribution of all isomers could be determined by the NMR spectroscopic results.

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) catalyzed esterification with 1-bromooctane over tetrakis/octakis(carboxy)phthalocyanines originated from trimellitic anhydride and pyromellitic dianhydride led to the isolation of a series of 2(3),9(10),16(17),24(25)-tetrakis(octyloxycarbonyl)phthalocyaninato metal complexes M[Pc(COOC8H17)4] (MCo, Ni, Cu, Zn) (1a–1d) and 2,3,9,10,16,17,24,25-octakis(octyloxycarbonyl)phthalocyaninato metal complexes M[Pc(COOC8H17)8] (MCo, Cu) (2a, 2c). In addition to elemental analysis, these tetrakis/octakis(octyloxycarbonyl)-substituted phthalocyanines were characterized by a series of spectroscopic methods including MALDI-TOF mass, 1H NMR and 2D COSY, UV–vis, and IR spectroscopy. The tetrakis(octyloxycarbonyl)-substituted phthalocyanines represent the first example of 2(3),9(10),16(17),24(25)-tetrakis(octyloxycarbonyl)phthalocyaninato metal complexes that have ever been unambiguously characterized by mass and NMR spectroscopy.Tetrakis- and octakis-(octyloxycarbonyl)phthalocyaninato metal complexes isolated from trimellitic anhydride and pyromellitic dianhydride have been unambiguously characterized by a wide range of spectroscopic techniques, providing a reliable method for the synthesis of corresponding phthalocyanine compounds.Highlights► Phthalocyanines were synthesized from trimellitic anhydride/pyromellitic dianhydride. ► Synthesis octyloxycarbonyl substituted phthalocyanines by esterification reaction. ► Characterized by elemental analysis, MALDI-TOF mass, UV–vis, IR and NMR spectroscopy

Four cyanide-bridged heterometallic complexes {[CuPb(L1)][FeIII(bpb)(CN)2]}2·(ClO4)2·2H2O·2CH3CN (1), {[CuPb(L1)]2[FeII(CN)6](H2O)2}·10H2O (2), {[Cu2(L2)][FeIII(bpb)(CN)2]2}·2H2O·2CH3OH (3) and {[Cu2(L2)]3[FeIII(CN)6]2(H2O)2}·10H2O (4) have been synthesized by treating K[FeIII(bpb)(CN)2] [bpb2−=1,2-bis(pyridine-2-carboxamido)benzenate] and K3[FeIII(CN)]6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L1)]·(ClO4)2 or [Cu2(L2)]·(ClO4)2, in which H2L1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H2L2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeIII(bpb)(CN)2]− and [CuPb(L1)]2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6]4− anion sandwiched in two [CuPu(L1)]2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu2(L2)]2+ segment and two terminal cyanide-containing blocks [FeIII(bpb)(CN)2]−. Octanuclear compound 4 is built from two [Fe(CN)6]3− anions sandwiched in the three [Cu2L2]2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.

Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H2TAP (A0B0C0D0) to naphthalocyanine H2Nc (A2B2C2D2) via phthalocyanine H2Pc (A1B1C1D1). All the transition paths of sixteen different compounds (A0B0C0D0–A2B2C2D2 and A0B0CmDn, m ≤ n ≤ 3) are fully optimized at the B3LYP/6-31G(d) level and vibration analyses have been conducted to verify the optimized structures. It is revealed that the number and position of fused benzene rings onto the TAP skeleton have significant effect on the potential energy barrier of the inner hydrogen atom transfer. Introducing fused benzene rings onto the hydrogen-releasing pyrrole rings can increase the transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer intermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N–H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.