Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand
09 Dec 2013-Vol. 1, Iss: 1, pp 32-45
TL;DR: In this article, the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand has been used to construct ruthenium-based mononuclear complexes with a specific coordination space.
Abstract: It is extremely important for synthetic chemists to control the structure of new compounds We have constructed ruthenium-based mononuclear complexes with the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand to investigate a new synthetic approach using a specific coordination space The synthesis of a family of new ruthenium complexes containing both the dnp and triphenylphosphine (PPh3) ligands, [Ru(dnp)(PPh3)(X)(L)]n+ (X = PPh3, NO2−, Cl−, Br−; L = OH2, CH3CN, C6H5CN, SCN−), has been described All complexes have been spectroscopically characterized in solution, and the nitrile complexes have also been characterized in the solid state through single-crystal X-ray diffraction analysis Dnp in the present complex system behaves like a “molecular sieve” in ligand replacement reactions Both experimental data and density functional theory (DFT) calculations suggest that dnp plays a crucial role in the selectivity observed in this study The results provide useful information toward elucidating this facile and selective synthetic approach to new transition metal complexes
Citations
More filters
TL;DR: In this paper, four new lead-II-iridium-III heterobimetallic coordination frameworks, i.e., [Pb2(L)4(DMF)2]·ClO4·2DMF·13H2O (1·DMF), [Pp(L,H2]2·H 2O]·3C3H6O·3H2 O·CH3CN (2·Acetone), and [Pm4(L]4I4·[Pb]10H2
Abstract: Four new lead(II)–iridium(III) heterobimetallic coordination frameworks, i.e., [Pb2(L)4(DMF)2]·ClO4·2DMF·13H2O (1·DMF), [Pb(L)2·H2O]·ClO4·3C3H6O·3H2O (1·Acetone), [Pb(L)2·H2O]·3C3H6O·3H2O·CH3CN (2·Acetone), and [Pb4(L)4I4·(DMF)2]·10H2O (3·DMF), where is L-H2 = Ir(ppy)2(H2dcbpy)PF6, ppy = 2-phenylpyridine, and H2dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, have been synthesized and structurally characterized using elemental analyses, IR spectroscopy, optical spectroscopy, and single-crystal X-ray diffraction. Heavy atoms, i.e. lead(II) atoms, were introduced to the frameworks and coordinated with the chromophore to promote an efficient intersystem crossing from the singlet to the triplet 3MLCT excited state and further promote sensitivity to oxygen. The emissions of 1·DMF, 1·Acetone, 2·Acetone and 3·DMF (referred to hereafter as 1·DMF–3·DMF) were ascribed to metal-to-ligand charge transfer transitions (MLCTs). These four compounds, using phosphorescence based detection, were able to detect oxygen sensitively in real gas, and their noteworthy oxygen-sensing properties were also evaluated. The quenching constants, or KSV values, between 1·DMF–3·DMF and oxygen, can be deduced to be 1.44, 1.60, 2.85, and 5.11, respectively. The minimum detectable concentrations (LODs) of oxygen for 1·DMF–3·DMF were calculated to be 0.65%, 0.70%, 0.61%, and 0.52%, respectively, from three times the signal to noise ratio. Moreover, taking 3·DMF as an example, short response (50 s) and recovery times (24 s) toward oxygen have been measured. It should be noted that the evaluated recovery time for 3·DMF is even shorter than those reported for rare-earth MOF films. The gas sensing properties, including sensitivity, sensing linearity, reproducibility, matrix effect, cross-sensitivity effect, temperature effect, and long-term stability, were investigated. Finally, in order to spark a broad spectrum of interest in terms of an application, 3·DMF was mixed with a commercial dye, Coumarin 480 (C480), to form a ratiometric oxygen sensor for the analysis of real gas in air.
37 citations
TL;DR: In this paper, the coordination chemistry of polypyridine-derived ligands is discussed, with particular focus on their ligand-centered redox properties originating from the attachment of redox-responsive 1,8-naphthyridine functional groups.
9 citations
TL;DR: In this paper, the tridentate polypyridyl type ligand (2,6-di(1,8-naphthyridin-2-yl)pyridine; dnp) with non-coordinating nitrogen atoms was used for the development of specific reactions using noncovalent interactions.
3 citations
17 Oct 2014
TL;DR: The Special Issue of Inorganics as discussed by the authors is the first issue dedicated to Innovative Inorganic Synthesis (IIS) and was published in 2003. [...] and the first themed issue of the journal and one dedicated to innovative organic synthesis.
Abstract: I am delighted to introduce this Special Issue of Inorganics; the first themed issue of the journal and one dedicated to Innovative Inorganic Synthesis. [...]
1 citations
TL;DR: In this article, a methoxy-substituted 2,6-di(1,8-naphthyridin-2-yl)pyridine was synthesized using Friedlander methodology.
References
More filters
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
Abstract: Despite the remarkable thermochemical accuracy of Kohn–Sham density‐functional theories with gradient corrections for exchange‐correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], we believe that further improvements are unlikely unless exact‐exchange information is considered. Arguments to support this view are presented, and a semiempirical exchange‐correlation functional containing local‐spin‐density, gradient, and exact‐exchange terms is tested on 56 atomization energies, 42 ionization potentials, 8 proton affinities, and 10 total atomic energies of first‐ and second‐row systems. This functional performs significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
87,732 citations
"Facile and Selective Synthetic Appr..." refers methods in this paper
...The ground-state, gas-phase structures of these complexes were optimized at the DFT level (B3LYP) [19,20]....
[...]
...gas-phase structures of these complexes were optimized at the DFT level (B3LYP) [19,20]....
[...]
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Abstract: A correlation-energy formula due to Colle and Salvetti [Theor. Chim. Acta 37, 329 (1975)], in which the correlation energy density is expressed in terms of the electron density and a Laplacian of the second-order Hartree-Fock density matrix, is restated as a formula involving the density and local kinetic-energy density. On insertion of gradient expansions for the local kinetic-energy density, density-functional formulas for the correlation energy and correlation potential are then obtained. Through numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, it is demonstrated that these formulas, like the original Colle-Salvetti formulas, give correlation energies within a few percent.
84,646 citations
"Facile and Selective Synthetic Appr..." refers methods in this paper
...The ground-state, gas-phase structures of these complexes were optimized at the DFT level (B3LYP) [19,20]....
[...]
...gas-phase structures of these complexes were optimized at the DFT level (B3LYP) [19,20]....
[...]
Book•
01 Jan 1978TL;DR: In this article, the normal modes of vibration are illustrated and corresponding vibrational frequencies are listed for each type, including diatomic, triatomic, fouratomic, five-atomic, six-atomic and seven-atomic types.
Abstract: Inorganic molecules (ions) and ligands are classified into diatomic, triatomic, four-atomic, five-atomic, six-atomic, and seven-atomic types, and their normal modes of vibration are illustrated and the corresponding vibrational frequencies are listed for each type. Molecules of other types are grouped into compounds of boron, carbon, silicon, nitrogen, phosphorus, and sulfur, and the structures and infrared (IR)/Raman spectra of select examples are shown for each group. Group frequency charts including band assignments are shown for phosphorus and sulfur compounds. Other group frequency charts include hydrogen stretching frequencies, halogen stretching frequencies, oxygen stretching and bending frequencies, inorganic ions, and metal complexes containing simple coordinating ligands.
Keywords:
inorganic compounds;
coordination compounds;
diatomic molecules (ligands);
triatomic molecules (ligands);
four-atomic molecules (ligands);
five-atomic molecules (ligands);
six-atomic molecules (ligands);
seven-atomic molecules (ligands);
boron compounds;
carbon compounds;
silicon compounds;
nitrogen compounds;
phosphorus compounds;
sulfur compounds;
group frequency charts
15,951 citations
"Facile and Selective Synthetic Appr..." refers background in this paper
...Two characteristic bands in the fingerprint region (1438 and 1304 cm) from the IR (infrared) spectrum of 5 suggest that 5 is a nitrogen atom-coordinated nitro species [11,12]....
[...]
TL;DR: In this article, two extended basis sets (termed 5-31G and 6 -31G) consisting of atomic orbitals expressed as fixed linear combinations of Gaussian functions are presented for the first row atoms carbon to fluorine.
Abstract: Two extended basis sets (termed 5–31G and 6–31G) consisting of atomic orbitals expressed as fixed linear combinations of Gaussian functions are presented for the first row atoms carbon to fluorine. These basis functions are similar to the 4–31G set [J. Chem. Phys. 54, 724 (1971)] in that each valence shell is split into inner and outer parts described by three and one Gaussian function, respectively. Inner shells are represented by a single basis function taken as a sum of five (5–31G) or six (6–31G) Gaussians. Studies with a number of polyatomic molecules indicate a substantial lowering of calculated total energies over the 4–31G set. Calculated relative energies and equilibrium geometries do not appear to be altered significantly.
13,036 citations
"Facile and Selective Synthetic Appr..." refers methods in this paper
...The 6-31G(d) basis set was employed for H, C, N, P, and Cl atoms [23,24]....
[...]
TL;DR: SIR97 is the integration of two programs, SIR92 and CAOS, the first devoted to the solution of crystal structures by direct methods, the second to refinement via least-squares–Fourier procedures.
Abstract: SIR97 is the integration of two programs, SIR92 and CAOS, the first devoted to the solution of crystal structures by direct methods, the second to refinement via least-squares–Fourier procedures. Several new features have been introduced in SIR97 with respect to the previous version, SIR92: greater automatization, increased efficiency of the direct methods section, and a powerful graphics interface. The program also provides publication tables and CIF files.
8,807 citations
"Facile and Selective Synthetic Appr..." refers methods in this paper
...The structures were solved by direct methods [29,30] and were expanded using Fourier techniques....
[...]