Effect of pH in the photoluminescence of a ruthenium complex featuring a derivative of the ligand pyrazine[2,3-f][1,10]-phenanthroline

Pizarro, Sebastián; Gallardo, Miguel; Leyton, Constanza; Castro, Eileen; Gajardo, Francisco; Delgadillo, Álvaro

doi:10.1016/j.saa.2015.03.067

Cited by 6 publications

(5 citation statements)

References 24 publications

(32 reference statements)

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“…To investigate the relationship between energy and structure, density functional theory (DFT) calculations were performed on the basis of M06-2X-D3/6-311G(d) using the Gaussian 09 D.01 software package. 37 We calculated the single-point energy of each linker in the three compounds. Because all of the linkers in PCN-206, PCN-207, and simulated PCN-208 share the same composition and similar (4,8)-connected Zr 6 clusters, the energy difference between each set of linkers is attributed to the structural differences.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Fabrication of (4, 10) and (4, 12)-Connected Multifunctional Zirconium Metal–Organic Frameworks for the Targeted Adsorption of a Guest Molecule

Zhang

Guo

et al. 2019

Inorg. Chem.

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Following the principle of a topology guide, a zirconium MOF (PCN-207) based on the H 4 TPTA ligand (tetramethyl(4,4′,4″,4‴-(pyrazine-2,3,5,6-tetrayl))tetrabenzoic acid) with C 2 symmetry and an 8-connected Zr 6 (μ 3-OH) 8 (OH) 8 ] 8+ cluster with D 4h symmetry has been synthesized. PCN-206 can also be obtained by modulating the benzoic acid usage to change the flexibility of the H 4 TPTA ligand. The unique positions of 8-connected Zr 6 clusters in the flu and scu networks and the flexibility of the tetratopic primary linker enable the precise insertion of fumarate (FA), 1,4-benzenedicarboxylic acid (H 2 BDC), and even 2,6-naphthalenedicarboxylic acid (H 2 NDC) in a one-pot reaction. Auxiliary linkers are used to generate new MOF structures or topologies or to split the pore spaces, which may significantly change the porosity and chemical and physical properties of scaffold MOFs. The results provide a successful strategy for the rational design of multicomponent Zr-MOFs. Because of differences in composition and configuration between structures, PCN-207 shows the highest separation capability of light hydrocarbons; moreover, PCN-206 exhibits the highest adsorption capacity of 2,4-D and DCF among MOFs at present.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Fabrication of (4, 10) and (4, 12)-Connected Multifunctional Zirconium Metal–Organic Frameworks for the Targeted Adsorption of a Guest Molecule

Zhang

Guo

et al. 2019

Inorg. Chem.

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“…The steadystate emission spectra were recorded on an Edinburgh FLS920 time-resolved fluorescence spectrometer at 298 K in H 2 O, using a 1 cm path length quartz cell. Time-correlated single-photoncounting (TCSPC) measurements were used for the luminescence decay of the ruthenium complex at different pHs (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). The luminescence quantum yields (j) were calculated by employing eqn (1), 15,16 using [Ru(bpy) 3 (PF 6 ) 2 ] as the standard.…”

Section: Spectroscopic Analysesmentioning

confidence: 99%

“…We also conducted a luminescence experiment to determine the behaviour of the emission of the complex in water at various pHs (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). Fig.…”

Section: Experiments On Absorption and Luminescence Spectroscopymentioning

confidence: 99%

“…36 The ruthenium complex is excited to singlet 1 MLCT states upon optical excitation and will efficiently cross-over to the light emitting triplet 3 MLCT (phosphorescence) state, which then returns to the ground state either by radiative (k r ) or nonradiative (k nr ) decay processes. The values of j, t r , t m , k r and k nr at different pH (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11) are catalogued and shown in Table 1. The emission quantum yield decreases as the pH increases owing to the increase in k nr and decrease in k r .…”

Section: Experiments On Absorption and Luminescence Spectroscopymentioning

confidence: 99%

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Augmented pH-sensitivity absorbance of a ruthenium(ii) bis(bipyridine) complex with elongation of the conjugated ligands: an experimental and theoretical investigation

Tan

Yanagisawa

Inagaki

et al. 2017

Phys. Chem. Chem. Phys.

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An absorbance-based sensor employing ruthenium bipyridyl with a phenanthroline-fused benzoylthiourea moiety formulated as [Ru(ii)(bpy)(phen-nBT)](PF) {bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, nBT = n-benzoylthiourea} has been synthesized and characterized by elemental analyses, mass spectrometry, and infrared, ultraviolet-visible, luminescence and nuclear magnetic resonance spectroscopy. The changes in the intensity of absorption and emission of the complex induced by functionalization of the benzoylthiourea ligands with amino and carbonyl in their protonated and deprotonated forms were studied experimentally. The absorption and emission properties of the complex exhibit a strong dependence on the pH (1-11) of the aqueous medium. This work highlights the pH-sensitivity augmentation of the absorption band by elongating the conjugation length in the structure of the ruthenium bipyridine complex. The principle of this work was to design the title compound to be capable of enhancing the differences in the absorption sensitivity responses towards pH between the protonated and deprotonated complexes in the absorption measurement. Along with significant and noticeable changes in the absorption spectra, subsequent theoretical investigations specifically on the electronic and absorbance properties of the title compound were carried out in this study. Protonation of the molecule significantly stabilized the lowest-unoccupied molecular orbital (LUMO), whereas the highest-occupied molecular orbital (HOMO) is greatly destabilized upon deprotonation. A time-dependent density functional theory (TDDFT) calculation in the linear-response (-LR) regime was performed to clarify the origin of the experimentally observed linear dependence of absorption intensity upon pH (1-11). The MLCT band exhibits hyperchromic shift at low pH as indicated by the large transition dipole moment and a wider distribution of the response charge of the molecule, which is induced by the stabilization of the electrostatic potential at the carbonyl moiety by protonation. This study provides the possibility of employing theoretical information to gain insight into the origin of the optical absorption obtained experimentally. The ruthenium complex was designed with an elongated ligand conjugation length and exhibited a tremendously large change in the absorption intensity of the protonated and deprotonated forms, which therefore demonstrates its feasibility as an indicator molecule especially for absorbance measurements.

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Development of a lysosome-targeted iridium (III) complex-based fluorescent probe for detection of HOCl and its application in living cells and water samples

Mao

et al. 2023

Inorganica Chimica Acta

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Effect of pH in the photoluminescence of a ruthenium complex featuring a derivative of the ligand pyrazine[2,3-f][1,10]-phenanthroline

Cited by 6 publications

References 24 publications

Fabrication of (4, 10) and (4, 12)-Connected Multifunctional Zirconium Metal–Organic Frameworks for the Targeted Adsorption of a Guest Molecule

Fabrication of (4, 10) and (4, 12)-Connected Multifunctional Zirconium Metal–Organic Frameworks for the Targeted Adsorption of a Guest Molecule

Augmented pH-sensitivity absorbance of a ruthenium(ii) bis(bipyridine) complex with elongation of the conjugated ligands: an experimental and theoretical investigation

Development of a lysosome-targeted iridium (III) complex-based fluorescent probe for detection of HOCl and its application in living cells and water samples

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