Rigid trisporphyrin with 1,3,5-triazine core: Synthesis, spectroscopy, and DABCO-induced self-assembly properties

A rigid Zn–trisporphyrin (1), the Zinc complex of 2,4,6-tris(5,10,15-triphenylporphyrinatozinc)-1,3,5-triazine (2) with three porphyrin moieties bridged by a rigid 1,3,5-triazine group, was synthesized and characterized by a series of spectroscopic methods including mass, 1H NMR, electronic absorption, and IR spectroscopy in addition to elemental analysis. The UV-vis spectrophotometric titration results revealed that along with the addition of the 1,4-diazabicyclo[2.2.2]octane (DABCO) form 0 to 3 equiv, 1 could form a 2:3 sandwich-type coordination cage in chloroform, which then transformed into a 1:3 open complex when the DABCO concentration was more than 3 equiv. Such DABCO-induced self- and disassembly processes were also confirmed by 1H NMR spectrophotometric titrations. In particular, it was demonstrated by comparative studies that the synergistic effect of the three porphyrin moieties linked together by the rigid 1,3,5-triazine group in 1 promoted the formation and stabilization of the 2:3 sandwich-type coordination cage. This result will be helpful towards the fabrication of various self-assembly structures based on metalloporphyrins with application potential in diverse areas such as molecular recognition and separation.

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DABCO-Directed Self-Assembly of Pyrene-Centered Porphyrin Pentamers

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.575-576.123 ◽

2013 ◽

Vol 575-576 ◽

pp. 123-129

Author(s):

Zhuang Dong Yuan ◽

Jing Xia Wang ◽

Ning Sheng

Keyword(s):

Self Assembly ◽

Fluorescence Emission ◽

The Self ◽

Spectroscopic Methods ◽

Assembly Process ◽

Zinc Porphyrin ◽

Axial Coordination ◽

H Nmr ◽

Wide Range ◽

Nmr Techniques

DABCO (1, 4-diazabicyclo [2.2.2] octane) has been used in combination with pentameric zinc porphyrin-pyrene array 1 to form well-defined supramolecular arrays through axial coordination. The self-assembly process has been investigated by a wide range of spectroscopic methods including UV-vis, fluorescence emission and 1H NMR techniques.

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Synthesis of metal-free and zinc phthalocyanines containing 2-pyridyl-methyl pendant arm linked with NS4-donor macrocyclic moiety and their selectivity towards Cu(II) cations

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424613500600 ◽

2013 ◽

Vol 17 (06n07) ◽

pp. 480-488 ◽

Cited By ~ 2

Author(s):

Nilgün Kabay ◽

Ümmühan Ocak ◽

Serhat Gün ◽

Yaşar Gök

Keyword(s):

Spectrophotometric Titration ◽

Spectroscopic Properties ◽

Zinc Phthalocyanine ◽

The Novel ◽

Metal Free ◽

H Nmr ◽

Pendant Arm ◽

Zinc Phthalocyanines ◽

Spectrophotometric Titrations ◽

Titration Data

New phthalonitrile (L1), metal-free phthalocyanine (H2Pc) and zinc-phthalocyanine (ZnPc) substituted in peripheral positions with 2-pyridyl methyl pendant arm linked mixed donor macrocyclic ligands have been prepared in a multi-step reaction sequence. The novel compounds were characterized by a combination of elemental anlaysis, 1 H NMR, 13 C NMR, IR, UV-vis and MS spectral data. The influence of metal cations such as Cd 2+, Zn 2+, Hg 2+, Al 3+, Fe 3+ and Cu 2+ on the spectroscopic properties of dinitrile compound L1 and free phthalocyanine H2Pc was investigated by means of absorption spectrophotometry. Spectrophotometric titrations were carried out with these ligands for Cu 2+ ion. The complex composition of Cu - L1 was found 1:1 by means of spectrophotometric titration data. The spectrophotometric method showed good sensitivity for Cu 2+ with linear range of 2.6 × 10-6 to 1.3 × 10-4 M with dinitrile compound.

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A new benzothiazin-functionalized calix[4]arene-based fluorescent chemosensor for the selective and sensitive detection of Co2+ ion

10.21203/rs.3.rs-259446/v1 ◽

2021 ◽

Author(s):

Fatimah Fateh ◽

Ayşe Yildirim ◽

Asif Ali Bhatti ◽

Mustafa YILMAZ

Keyword(s):

Organic Chemistry ◽

Detection Limit ◽

Ir Spectroscopy ◽

Binding Constant ◽

Spectroscopic Methods ◽

Macrocyclic Compounds ◽

H Nmr ◽

Ft Ir ◽

Ft Ir Spectroscopy ◽

C Nmr

Abstract Calixarenes, which have a great place in supramolecular chemistry, has become the most prominent macrocyclic compounds in synthetic organic chemistry due to their easy synthesis and functionalization. In this study, p-tert-butyl calix[4]arene dihydrazide derivative was synthesized and then reacted with 3-oxo-3,4-dihydro-2H-benzo[b][1, 4] thiazin-2-ylideneacetyl chloride to prepare new calixarene based chromophore compound 4. The structure of the synthesized compound was elucidated by spectroscopic methods such as 1H-NMR 13C-NMR and FT-IR spectroscopy. Chromogenic and fluorescence properties of compound 4 were evaluated. It was observed from both studies that compound 4 was Co2+ selective and shows fluorescence Switched-off behavior. Stoichiometry, binding constant and the detection limit was calculated. The stoichiometry between compound 4 and Co2+ was found to be 1:1. The binding constant value (K) was calculated as 666.67 M− 1 using Benesi–Hildebrand equation, while the detection limit for Co2+ ion was calculated as 0.0465 µM.

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Electrochemically Synthesis and Characterization of Copolymers Based on 1, 4-Diethoxybenzene and 3, 4-Ethylenedioxythiophene

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.335-336.989 ◽

2011 ◽

Vol 335-336 ◽

pp. 989-993

Author(s):

Mi Ouyang ◽

Zhen Wei Yu ◽

Yi Xu ◽

Yu Jian Zhang ◽

Cheng Zhang

Keyword(s):

Cyclic Voltammetry ◽

Ir Spectroscopy ◽

Feed Ratio ◽

Synthesis And Characterization ◽

Monomer Mixture ◽

Long Wavelength ◽

H Nmr ◽

Ft Ir ◽

Ft Ir Spectroscopy

Copolymers based on 1, 4-diethoxybenzene (DEB) and 3, 4-ethylenedioxythiophene (EDOT) were electrochemically synthesized and characterized. The structures of the copolymers were established by 1H NMR and FT-IR spectroscopy. The results indicated the final product was a copolymer instead of a blend or a composite. The physical properties were systematically investigated by cyclic voltammetry, UV-vis absorption and fluorescence. The PL maximum of copolymers presented obviously red-shift to long wavelength as the feed ratio of EDOT in monomer mixture increased.

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Self-Assembly of a Family of Isopolytungstates Induced by the Synergistic Effect of the Nature of Lanthanoids and the pH Variation in the Reaction Process: Syntheses, Structures, and Properties

Crystal Growth & Design ◽

10.1021/acs.cgd.5b00996 ◽

2015 ◽

Vol 16 (1) ◽

pp. 108-120 ◽

Cited By ~ 20

Author(s):

Hailou Li ◽

Wen Yang ◽

Xiuhua Wang ◽

Lijuan Chen ◽

Jianru Ma ◽

...

Keyword(s):

Synergistic Effect ◽

Self Assembly ◽

Reaction Process ◽

Ph Variation ◽

Structures And Properties

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Synergistic effect of sandwich polyoxometalates and copper–imidazole complexes for enhancing the peroxidase-like activity

RSC Advances ◽

10.1039/c5ra13265g ◽

2015 ◽

Vol 5 (96) ◽

pp. 78771-78779 ◽

Cited By ~ 23

Author(s):

Dong-Feng Chai ◽

Zhuo Ma ◽

Hong Yan ◽

YunFeng Qiu ◽

Hong Liu ◽

...

Keyword(s):

Synergistic Effect ◽

Sandwich Polyoxometalates ◽

Imidazole Complexes ◽

Sandwich Type

Two inorganic–organic hybrids based on copper(ii)–imidazole complex modified sandwich-type tungstobismuthate or tungstoantimonite, have been synthesized, demonstrating higher peroxidase-like activity using TMB as a peroxidase substrate.

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Linkage of α-cyclodextrin-terminated poly(dimethylsiloxanes) by inclusion of quasi bifunctional ferrocene

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.9.144 ◽

2013 ◽

Vol 9 ◽

pp. 1278-1284 ◽

Cited By ~ 2

Author(s):

Helmut Ritter ◽

Berit Knudsen ◽

Valerij Durnev

Keyword(s):

Electron Microscopy ◽

Mass Spectrometry ◽

Light Scattering ◽

Ir Spectroscopy ◽

Nmr Spectra ◽

H Nmr ◽

Scattering Measurements ◽

End Groups ◽

2D Roesy ◽

2D Roesy Nmr

We report the noncovalent linkage of terminally substituted oligo(dimethylsiloxanes) bearing α-cyclodextrins (α-CD) as host end groups for the cyclopentadienyl rings of ferrocene. This double complexation of unsubstituted ferrocene leads to a supramolecuar formation of the siloxane strands. Structural characterization was performed by the use of 1H NMR and IR spectroscopy and by mass spectrometry. Electron microscopy studies and dynamic light scattering measurements show a significant decrease of the derivative size after the complexation with ferrocene. In addition, further evidence for the successful complexation of the end groups was verified by the shifts of the protons in the 1H NMR spectra and in the correlation signals of the 2D ROESY NMR spectra.

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The Research of G–Motif Construction and Chirality in Deoxyguanosine Monophosphate Nucleotide Complexes

Frontiers in Chemistry ◽

10.3389/fchem.2021.709777 ◽

2021 ◽

Vol 9 ◽

Author(s):

Yanhong Zhu ◽

Zhongkui Li ◽

Pengfei Wang ◽

Qi–Ming Qiu ◽

Hongwei Ma ◽

...

Keyword(s):

Solid State ◽

Self Assembly ◽

Genetic Diseases ◽

Dna Interaction ◽

Wave Direction ◽

Base Pairing ◽

X Ray Crystallography ◽

Mismatched Dna ◽

H Nmr ◽

Guanine Base

A detailed understanding of the mismatched base-pairing interactions in DNA will help reveal genetic diseases and provide a theoretical basis for the development of targeted drugs. Here, we utilized mononucleotide fragment to simulate mismatch DNA interactions in a local hydrophobic microenvironment. The bipyridyl-type bridging ligands were employed as a mild stabilizer to stabilize the GG mismatch containing complexes, allowing mismatch to be visualized based on X-ray crystallography. Five single crystals of 2′-deoxyguanosine–5′–monophosphate (dGMP) metal complexes were designed and obtained via the process of self-assembly. Crystallographic studies clearly reveal the details of the supramolecular interaction between mononucleotides and guest intercalators. A novel guanine–guanine base mismatch pattern with unusual (high anti)–(high anti) type of arrangement around the glycosidic angle conformations was successfully constructed. The solution state 1H–NMR, ESI–MS spectrum studies, and UV titration experiments emphasize the robustness of this g–motif in solution. Additionally, we combined the methods of single-crystal and solution-, solid-state CD spectrum together to discuss the chirality of the complexes. The complexes containing the g–motif structure, which reduces the energy of the system, following the solid-state CD signals, generally move in the long-wave direction. These results provided a new mismatched base pairing, that is g–motif. The interaction mode and full characterizations of g–motif will contribute to the study of the mismatched DNA interaction.

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Side Chain Influence on Main Chain Orientation of PPV-Type Oligomers

MRS Proceedings ◽

10.1557/proc-598-bb3.16 ◽

1999 ◽

Vol 598 ◽

Author(s):

Ruth Müllner ◽

Laurence Noirez ◽

Egbert Zojer ◽

Franz Stelzer ◽

Günther Leising

Keyword(s):

Magnetic Field ◽

Neutron Diffraction ◽

Main Chain ◽

Side Chain ◽

Phenylene Vinylene ◽

Spectroscopic Methods ◽

Polarized Optical Microscopy ◽

Chain Orientation ◽

H Nmr ◽

Ft Ir

ABSTRACTOligo (p-phenylene vinylene)s OPV were synthesized having cyanobiphenyloxy-groups bonded to the vinylene double bonds via alkylene spacers. A Pd(0)-reaction was used to synthesize the oligomers starting with the dibromo-substituted benzene and the alkenyloxy-biphenyl-nitrile. The orientation of the mesogens by a magnetic field and their influence on the orientation of the main chain was investigated by means of neutron diffraction ND. Data on the photophysics of the oligomers were gained using several spectroscopic methods such as UV/VIS, polarized optical microscopy POM, SEC, 1H-NMR, FT-IR.

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