Tungsten and molybdenum oxo complexes of tetrakis(phenyldiazenyl)calix[4]arene substituted derivatives: EHMO calculations, spectroscopic characterization, and perturbations of the photophysical properties by neutral guest molecules

1996 ◽  
Vol 74 (11) ◽  
pp. 2279-2288 ◽  
Author(s):  
Pierre D. Harvey ◽  
Jonathan Gagnon ◽  
Réjean Provencher ◽  
Bing Xu ◽  
Timothy M. Swager
Keyword(s):  
Excited States ◽  
Photophysical Properties ◽  
Binding Constants ◽  
Spectroscopic Characterization ◽  
Guest Molecules ◽  
H Nmr ◽  
Oxo Complexes ◽  
Visible Luminescence ◽  
Uv Visible ◽  
Host Chemistry

Bowl-shaped chromophores fabricated with tungsten and molybdenum oxo complexes of calix[4]arenes substituted at the para positions with phenyldiazenyl (R2C6H3N2) derivatives are investigated. The nature of the lowest energy excited states has been addressed theoretically using Extended Hückel Molecular Orbital (EHMO) calculations and experimentally using UV-visible, luminescence, and polarized emission spectroscopy at 77 K. The lowest energy excited states are intraligand (azobenzene fragment) ππ* (S2 and T2) and ππ*states (S1, and T1). The compounds are weakly luminescent in the 600–630 nm range exhibiting emissions arising from the 1(ππ*) states [Formula: see text]. The region located above 900 nm was not investigated. Evidence for guest–host chemistry has been demonstrated by1H-NMR spectroscopy, and the binding constants for two of the compounds with pyridine in toluene as a solvent were obtained by UV–visible spectroscopy. The presence of a guest molecule inside the luminescent metal oxo complex of a calix[4]arene hosts decreases the emission lifetimes.Key words: host–guest, photophysics, calix[4]arene, EHMO, fluorescence

Tuning of the Cavity of Water-Soluble Thiacalix[4]arene for the Control of Inclusion Ability Toward Water-Miscible Organic Molecules

2004 ◽  
Vol 69 (5) ◽  
pp. 1080-1096 ◽  
Author(s):  
Noriyoshi Kon ◽  
Nobuhiko Iki ◽  
Yuichiro Sano ◽  
Satoshi Ogawa ◽  
Chizuko Kabuto ◽  
...  
Keyword(s):  
Guest Molecule ◽  
Organic Molecules ◽  
Hydrophobic Effect ◽  
Binding Constants ◽  
Water Soluble ◽  
Main Role ◽  
Diethyl Ketone ◽  
Guest Molecules ◽  
X Ray ◽  
H Nmr

Inclusion abilities of water-soluble thiacalix[4]arenetetrasulfonate (3) and mono-O-carboxymethylated derivatives 5 and 6 toward water-miscible organic molecules such as alcohols, ketones, and nitriles in water were investigated by 1H NMR. The limit chemical shift change of the guest upon inclusion in the host suggested that the hosts regioselectively encapsulate the guests from the side of aliphatic moiety. Large guests such as pentan-1-ol showed folding of the alkyl chain to be included inside the cavity. On the other hand, mono-O-substituted 6 included a guest molecule less deep in the cavity than 3 did. Binding constants (K) of 3 toward guest molecules increased with hydrophobicity of the guest, suggesting that hydrophobic effect plays a main role for the complexation. On the contrary, mono-O-carboxymethyl derivatives 5 and 6 showed the opposite dependency of stability on hydrophobicity; higher affinities toward less hydrophobic guests. Among the guests examined, the smallest entities such as CH3OH and CH3CN were best included in 5 with the highest binding constant ever reported (K > 102 M-1). It was concluded that introduction of the carboxymethyl group into one of the phenolic OH of thiacalix[4]arene led to tuning of the cavity shape for stereospecific inclusion of small guests. The tuning of cavity by the O-alkylation was actually confirmed by X-ray crystal analysis of a complex of 5 with diethyl ketone.

scholarly journals Synthesis and characterization of azo-guanidine based alcoholic media naked eye DNA sensor

2016 ◽  
Vol 3 (11) ◽  
pp. 160351 ◽  
Author(s):  
Ataf Ali Altaf ◽  
Uzma Hashmat ◽  
Muhammad Yousaf ◽  
Bhajan Lal ◽  
Shafiq Ullah ◽  
...  
Keyword(s):  
Binding Constants ◽  
Blue Shift ◽  
Dna Sensing ◽  
H Nmr ◽  
Naked Eye ◽  
Uv Visible ◽  
New Compounds ◽  
Synthesized Materials ◽  
Dna Binding Properties

DNA sensing always has an open meadow of curiosity for biotechnologists and other researchers. Recently, in this field, we have introduced an emerging class of molecules containing azo and guanidine functionalities. In this study, we have synthesized three new compounds ( UA1 , UA6 and UA7 ) for potential application in DNA sensing in alcoholic medium. The synthesized materials were characterized by elemental analysis, FTIR, UV-visible, 1 H NMR and 13 C NMR spectroscopies. Their DNA sensing potential were investigated by UV-visible spectroscopy. The insight of interaction with DNA was further investigated by electrochemical (cyclic voltammetry) and hydrodynamic (viscosity) studies. The results showed that compounds have moderate DNA binding properties, with the binding constants range being 7.2 × 10 3 , 2.4 × 10 3 and 0.2 × 10 3  M −1 , for UA1 , UA6 and UA7 , respectively. Upon binding with DNA, there was a change in colour (a blue shift in the λ max value) which was observable with a naked eye. These results indicated the potential of synthesized compounds as DNA sensors with detection limit 1.8, 5.8 and 4.0 ng µl −1 for UA1 , UA6 and UA7 , respectively.

Solvent Dependence of Structural Dynamics and Spin-flip Processes in 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (ortho-3CzBN)

2020 ◽  
Author(s):  
Masaki Saigo ◽  
Kiyoshi Miyata ◽  
Hajime Nakanotani ◽  
Chihaya Adachi ◽  
Ken Onda
Keyword(s):  
Dft Calculations ◽  
Excited States ◽  
Structural Changes ◽  
Photophysical Properties ◽  
Delayed Fluorescence ◽  
Time Resolved ◽  
Thermally Activated Delayed Fluorescence ◽  
Thermally Activated ◽  
Solvent Dependence ◽  
Acetonitrile Solutions

We have investigated the solvent-dependence of structural changes along with intersystem crossing of a thermally activated delayed fluorescence (TADF) molecule, 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (o-3CzBN), in toluene, tetrahydrofuran, and acetonitrile solutions using time-resolved infrared (TR-IR) spectroscopy and DFT calculations. We found that the geometries of the S1 and T1 states are very similar in all solvents though the photophysical properties mostly depend on the solvent. In addition, the time-dependent DFT calculations based on these geometries suggested that the thermally activated delayed fluorescence process of o-3CzBN is governed more by the higher-lying excited states than by the structural changes in the excited states.<br>

scholarly journals Unusual piezochromic fluorescence of a distyrylpyrazine derivative crystals: phase transition through [2 + 2] photocycloaddition under UV irradiation

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Young-Jae Jin ◽  
Hyosang Park ◽  
Byung-Chun Moon ◽  
Jae Hong Kim ◽  
Wang-Eun Lee ◽  
...  
Keyword(s):  
Phase Transition ◽  
Solid State ◽  
Uv Irradiation ◽  
Mechanical Grinding ◽  
Green Color ◽  
H Nmr ◽  
Uv Visible ◽  
Stacking Structure ◽  
Orange Color ◽  
Molecular Stacking

AbstractThe piezochromic fluorescence (FL) of a distyrylpyrazine derivative, 2,3-diisocyano-5,6-distyrylpyrazine (DSP), was investigated in this study. Depending on the recrystallization method, DSP afforded two different crystals with green and orange FL emission. The orange color FL emission crystal (O-form) was easily converted to the green color FL emission one (G-form) by manual grinding. The G-form was also converted to a slightly different orange color FL emission crystal (RO-form) by a weak UV irradiation. When the RO-form was ground again, the G-form was regenerated. The FL colors changed between the G- and RO-forms over several ten times by repeated mechanical grinding and UV irradiation. The FL, UV–visible, 1H-NMR and XRD results showed that the O (or RO)-to-G transformation induced by mechanical stress results from the change of degree of molecular stacking from dense molecular stacking structure to relatively loose molecular stacking structure, whereas the G-to-RO reconversion by UV irradiation results from return to dense molecular stacking structure again due to lattice movement (lattice slipping) allowed by photocycloaddition in solid-state.

scholarly journals Water-soluble β-aminobisulfonate building blocks for pH and Cu2+ indicators

RSC Advances ◽  
2016 ◽  
Vol 6 (88) ◽  
pp. 84712-84721 ◽  
Author(s):  
Maria A. Cardona ◽  
Marina Kveder ◽  
Ulrich Baisch ◽  
Michael R. Probert ◽  
David C. Magri
Keyword(s):  
Nmr Spectroscopy ◽  
Building Blocks ◽  
Water Soluble ◽  
Visible Absorption ◽  
H Nmr ◽  
Uv Visible

Two phenyl β-aminobisulfonate ligands characterised by UV-visible absorption, EPR and 1H NMR spectroscopy exhibit evidence for binding with Cu2+ in water and methanol.

Synthesis and properties of a sterically encumbered poly(thienylene vinylene): poly[E-1,2-(4,4prime-dihexyl-2,2prime-dithienyl)ethylene]

1998 ◽  
Vol 76 (11) ◽  
pp. 1524-1529
Author(s):  
Jimmy Lowe ◽  
Carl Bartels ◽  
Steven Holdcroft
Keyword(s):  
Ftir Spectroscopy ◽  
Electrically Conducting ◽  
H Nmr ◽  
Visible Photoluminescence ◽  
Micron Size ◽  
Visible Irradiation ◽  
Uv Visible ◽  
The Stability ◽  
Doped Polymer ◽  
Polythiophene Derivative

Electrically conducting poly[E-1,2-(4,4prime-dihexyl-2,2prime-dithienyl)ethylene] was synthesized and structurally characterized by UV-visible, 1H NMR, and FTIR spectroscopy. The head-to-head arrangement of the alkylthiophene dyads directly affects the UV-visible, photoluminescence, and electroluminescence maxima of the polymer. The conductivity of the doped polymer was measured to be ~2 S cm-1 and the stability of the oxidized polymer possessing various dopants was compared. UV-visible irradiation of PDHDTE rendered the films insoluble and photolithography was used to produce micron-size images. FTIR was used to monitor the photoproducts during photolysis of PDHDTE. Mechanisms of photooxidation were proposed, based on the photoproducts observed.Key words: polythiophene derivative, head-to-head dyad, photolithography, photooxidation, electroluminescence.

scholarly journals VUV-UV-visible luminescence of Nd3+, Er3+ and Tm3+ in LiLuF4 single crystal host

2010 ◽  
Vol 45 (3-6) ◽  
pp. 403-405 ◽  
Author(s):  
J. Martincik ◽  
M. Nikl ◽  
S. Ishizu ◽  
K. Fukuda ◽  
T. Suyama ◽  
...  
Keyword(s):  
Single Crystal ◽  
Visible Luminescence ◽  
Uv Visible

Synthesis, Characterization and Photophysical Properties of Rhenium(I) Complexes Containing 4,5-Diazafluorene Ligan

2011 ◽  
Vol 239-242 ◽  
pp. 2612-2615
Author(s):  
Jie Xiu Wang ◽  
Feng Zhao
Keyword(s):  
Charge Transfer ◽  
Fluorescence Spectra ◽  
Photophysical Properties ◽  
Absorption And Fluorescence Spectra ◽  
Rhenium Complexes ◽  
H Nmr ◽  
Ligand Charge Transfer

Two related tricarbonyl rhenium complexes with the formula of [Re(CO)3(L)Cl], where L=4,5-diazafluoren-9-one (Dafo-Re) and 9-(phenylamino)-4,5-diazafluoren (PADF-Re) were successfully synthesized with the aim to explore the effect of the geometry of Dafo on Rhenium(I) coordination, and characterized by1H NMR. Photophysical behaviors are investigated by UV–vis absorption and Fluorescence spectra. The two complexes Dafo-Re and PADF-Re show metal-to-ligand charge transfer absorptions at ca.391nm, ca.394 nm and emissions at ca.492nm, ca.470nm, respectively.

scholarly journals Interactions between 4-thiothymidine and water-soluble cyclodextrins: Evidence for supramolecular structures in aqueous solutions

2016 ◽  
Vol 12 ◽  
pp. 549-563 ◽  
Author(s):  
Vito Rizzi ◽  
Sergio Matera ◽  
Paola Semeraro ◽  
Paola Fini ◽  
Pinalysa Cosma
Keyword(s):  
Inclusion Complexes ◽  
Pyrimidine Ring ◽  
Protective Role ◽  
Supramolecular Structures ◽  
Water Soluble ◽  
Aqueous Environment ◽  
Spectroscopic Techniques ◽  
Guest Molecules ◽  
H Nmr ◽  
Cv Measurements

Since several years the inclusion of organic compounds (guests) within the hydrophobic cavity (host) of cyclodextrins (CDs) has been the subject of many investigations. Interestingly, the formation of inclusion complexes could affect the properties of the guest molecules and, for example, the influence of the delivery system can be a method to improve/change the photochemical behavior of the guest. In particular, very recent studies have shown the protective role of CDs preventing the degradation of the encapsulated guest. Starting from this consideration, in this work, only the structure and complexation mode of the inclusion complexes involving 4-thiothymidine (S4TdR, a known photosensitizer) and five CDs, namely 2-hydroxypropyl-α-cyclodextrin (2-HP-α-CD), 2-hydroxypropyl-β-cyclodextrin (2-HP-β-CD), 2-hydroxypropyl-γ-cyclodextrin (2-HP-γ-CD), heptakis-(2,6-di-O-methyl)-β-cyclodextrin (DIMEB CD) and heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (TRIMEB CD) were investigated by different spectroscopic techniques (UV–vis, FTIR–ATR, 1H NMR) and cyclic voltammetry analysis (CV). This work is necessary for a prospective research on the photoreactivity of S4TdR in aqueous environment and in the presence of CDs to prevent its degradation under irradiation. UV–vis, FTIR–ATR and CV measurements suggested the formation of supramolecular structures involving the employed CDs and mainly the pyrimidine ring of S4TdR. 1H NMR analyses confirmed such indication, unveiling the presence of inclusion complexes. The strongest and deepest interactions were suggested when TRIMEB and DIMEB CDs were studied. The S4TdR affinity towards CDs was also evaluated by using the Benesi–Hildebrand (B–H) equation at 25 °C employing CV and 1H NMR methods. The stoichiometry of the interaction was also inferred and it appears to be 1:1 for all examined CDs.

scholarly journals Synthesis, Characterization, and Biological Studies of a Piperidinyl Appended Dipicolylamine Ligand and Its Rhenium Tricarbonyl Complex as Potential Therapeutic Agents for Human Breast Cancer

2016 ◽  
Vol 2016 ◽  
pp. 1-10 ◽  
Author(s):  
Amali Subasinghe ◽  
Inoka C. Perera ◽  
Svetlana Pakhomova ◽  
Theshini Perera
Keyword(s):  
Breast Cancer ◽  
Anticancer Agents ◽  
Human Breast Cancer ◽  
Human Breast ◽  
Tricarbonyl Complex ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Biological Studies ◽  
Visible Spectra ◽  
Uv Visible

A novel ligand bearing a central piperidinyl sulfonamide group, N(SO2pip)dpa, and its corresponding Re tricarbonyl complex, [Re(CO)3(N(SO2pip)dpa)]+, have been synthesized in good yield. The methylene CH2signal seen as a singlet (4.54 ppm) in a1H NMR spectrum of the ligand in DMSO-d6appears as two doublets (5.39, 5.01 ppm) in a spectrum of the [Re(CO)3(N(SO2pip)dpa)]+complex and confirms the presence of magnetically nonequivalent protons upon coordination to Re. Structural results revealed that the Re–N bond lengths fall within the normal range establishing coordination of ligand to metal. The presence of intraligandπ→π⁎andn→π⁎transitions is indicated by the absorption peaks around 200–250 nm in UV-visible spectra. Absorption peaks in UV-visible spectra around 300 nm for metal complexes were identified as MLCT transitions. The S–N stretch observed as a strong peak at 923 cm−1for N(SO2pip)dpa appeared at a shorter frequency, at 830 cm−1in an FTIR spectrum of the [Re(CO)3(N(SO2pip)dpa)]+. The intense fluorescence displayed by the N(SO2pip)dpa ligand has quenched upon coordination to Re. Relatively low IC50values given by human breast cancer cells, MCF-7, (N(SO2pip)dpa = 139 μM, [Re(CO)3(N(SO2pip)dpa)]+= 360 μM) indicate that N(SO2pip)dpa and [Re(CO)3(N(SO2pip)dpa)]+are promising novel compounds that can be further investigated on their usage as potential anticancer agents.

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