Viscosity and Temperature Effects on the Rate of Oxygen Quenching of Tris-(2,2′-bipyridine)ruthenium(II)

We compare the bimolecular quenching rate constant (k₂) of luminescent tris(2,2′-bipyridine)ruthenium(II) by oxygen in water, ethylene glycol and glycerol as a function of temperature and viscosity to several theoretical models. The Smoluchowski equation with experimentally determined diffusion coefficients produced calculated values that were in the best agreement with experiment. For the less viscous solvent, water, this equation produced a value that was approximately an order of magnitude larger than the experimental value. With an increase in solvent viscosity, the Smoluchowski value approached the experimental value. Using the Smoluchowski equation with calculated diffusion coefficients based on the known radii of the reacting species produced deviations an order of magnitude larger in water and a factor of two or three lower in ethylene glycol and glycerol. If an assumption is made that the radii of both molecules are equal, we have the Stokes Einstein equation, and the only parameters become temperature and viscosity. Using this relationship, the calculated values for water are about a factor of two larger and with ethylene glycol and glycerol about a factor of 6 smaller than experimental data. These results show that bimolecular quenching is a more complex process affected by many parameters such as solvent cage effects in addition to viscosity and temperature.     

Optical and electrochemical properties of cyclometalated Rh(III) complexes based on 4,6-diphenylpyrimidine with ethylenediamine, 2,2′-bipyridyl,and 1,10-phenanthroline

The [Rh(Hdp)₂(N∧N)]ClO₄ complexes (Hdp⁻ is the monodeprotonated form of 4,6-diphenylpyrimidine and (N∧N) is ethylenediamine, 2,2′-bipyridyl, and 1,10-phenanthroline) are synthesized and characterized by ¹H and ¹³C NMR, IR, electronic absorption, and emission spectroscopy, as well as by cyclic voltammetry. The magnetic equivalence of two cyclometalated 4,6-diphenylpyrimidine ligands in the composition of complexes points to the cis position of metalated phenyl rings in the inner sphere. Quasi-reversible one-electron reduction waves are attributed to the ligand-centered electron transfer to the π* antibonding orbital of heterocyclic ligands, while irreversible oxidation waves are associated with electron detachment from the Rh-C σ bonding orbital of the {Rh(Hdp)₂} metal-complex fragment. The characteristic long-wave-length absorption bands and the vibrationally structured phosphorescence bands of complexes are assigned to the spin-allowed and spin-forbidden charge-transfer optical transitions between the σ_Rh-C and π_Hdp* orbitals localized on the {Rh(Hdp)₂} fragment of the complex.     

Theoretical study on the influence of different NˆN ligands on the electronic structures and optoelectronic properties of heteroleptic Iridium(III) complexes

DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and phosphorescence properties of a series of heteroleptic Ir(III) complexes consisting of two N-heterocyclic carbene ligands and a conjugated bicyclic N,N′-heteroaromatic (N?N) ligand. On the basis of the results reported herein, we attempt to explain the experimental observations according to which complex (mpmi)₂Ir(pybi) (1) [Hmpmi = 1-(4-tolyl)-3-methyl-imidazole; Hpybi = 2-(pyridin-2-yl)-1H-benzo[d]imidazole] emits green light with an extremely high-quantum phosphorescence efficiency (Φ _PL ) of 79.3%, while a relatively lower Φ _PL (only 11%) was measured for (fpmi)₂Ir(tfpypz) (2) [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C, C^2′; tfpypz = 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridinato] emitting blue light by tuning the N?N ligands. Besides, we also designed (fpmi)₂Ir(pyN3) (3) [pyN3H = 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] and (fpmi)₂Ir(pyN4) (4) [pyN4H = 2-(1H-tetrazol-5-yl)pyridine] to explore the influence of electron-withdrawing substituents on N?N ligands on the electronic and optical properties of these Ir(III) complexes. The results revealed that electron-withdrawing substituents can stabilise both HOMOs and LUMOs and induce HOMO–LUMO energy gap change. Moreover, the emission properties can be significantly tuned by introducing different N?N ligands. While new insights were gained on structural and electronic properties, the extremely high Φ _PL of 1 was found to be not inherent to spin-orbital coupling effects, but determined by its large transition dipole moment (μ_{S 1}) upon S ₀–S ₁ transition compared with that of 2. On the basis of these results, the designed complexes 3 and 4 are considered to be the promising candidates for blue-emitting phosphorescence materials with higher Φ _PL than the complex 2.     

Electrochemical behavior and DNA-binding properties of binuclear copper(II) complex containing mixed ligands of N-hydroxyethylaminoethyl oxamido and 2,2′-bipyridine

The electrochemical property of dinuclear copper(II) complex containing mixed ligands of N-hydroxyethylaminoethyl oxamido and 2,2′-bipyridine [Cu₂(bpy)₂(HAO) ₂ ²⁺ ] was studied with cyclic voltammetry. Cu₂(bpy)₂(HAO) ₂ ²⁺ had irreversible oxidation peaks in 0.1 mol/L NaCl solution at the stearic acid-modified carbon paste electrode. Cyclic voltammetry and absorption spectra measurements were used to study the interaction between Cu₂(bpy)₂(HAO) ₂ ²⁺ and herring fish sperm DNA. All the experimental results showed that Cu₂(bpy)₂(HAO) ₂ ²⁺ interacted with DNA mainly through electrostatic affinity to make tiny difference between Cu₂(bpy)₂(HAO) ₂ ²⁺ –ssDNA and Cu₂(bpy)₂(HAO) ₂ ²⁺ –dsDNA. The binding ratio and the binding constant of DNA–Cu₂(bpy)₂(HAO) ₂ ²⁺ were calculated as 1:1 and 6.41?×?10⁴, respectively. The redox peak current of Cu₂(bpy)₂(HAO) ₂ ²⁺ decreased markedly after its interaction with DNA. This was used to detect the concentration of DNA quantitatively.     

Magnetic-field and temperature effects on the optical properties of dicyano-2,2′-bipyridyl-platinum(II) single crystals

Studies of the polarized emission of [Pt(CN)₂(bipy)] single crystals as function of temperature (1.9 K ⩽ T ⩽ 295 K) and homogeneous magnetic fields (0 ⩽ H ⩽ 6 T), and the temperature dependence of the polarized absorption spectrum are reported. Raising the temperature from 1.9 to 7 K or increasing the magnetic field from 0 to 1 T results in a blue shift of ≈175 cm^-1 in the E ⊥ a polarized emission (E: electric field vector, a: crystallographic a axis). Between 1.9 and 295 K at H = 0) and between 0 and 6 T (at T = 1.9 K), the emission lifetime decreases by factors of ≈10³ and ≈10², respectively. The results are explained within the C'_2v symmetry of the single complex assuming a coupling between neighboring central ions.     

Synthesis and Spectral Studies of Novel Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) Metal Complexes with N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL)

Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) complexes with Schiff base derived from 2-amino-5-(2-amino-1,3,4-thiadiazolyl)-1,3,4-thiadiazole (1) and salicylaldehyde have been prepared. The ligand and its complexes have been characterized by IR, ¹H NMR spectra, elemental analyses, magnetic susceptibility, UV-Vis. and thermogravimetry–differential thermal analysis (TGA-DTA). The analytical data show 1:2 metal-to-ligand ratio for Co(II), Ni(II), Cd(II), and Fe(II) and 2:2 metal-to-ligand ratio for Cu(II) complexes. The suggested structures for the N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL) complexes of Fe(II), Co(II), and Cd(II) are octahedral, for the Ni(II) complex is tetrahedral, and for the Cu(II) complex is square-planar     

Theoretical studies on the electronic and optoelectronic properties of [A.2AP(w)/A*.2AP(WC)/C.2AP(w)/C*.2AP(WC)/C.A(w)/C*.A(WC)]–Au8 mismatch nucleobase complexes

The electronic and optoelectronic properties of [A.2AP(w)/A^*.2AP(WC)/C.2AP(w)/C^*.2AP(WC)/C.A(w)/ C^*.A(WC)]–Au₈ metal-mismatch nucleobase complexes are investigated by means of density functional theory and time-dependent methods. We selected these mispairs as 2-aminopurine (2AP) produces incorporation errors when binding with cytosine (C) into the wobble (w) C·2AP(w) mispair, and is tautomerised into Watson–Crick (WC)-like base mispair C^*·2AP(WC) and less effectively produces A.2AP(w)/A^*.2AP(WC) mispairs. The vertical ionisation potential, vertical electron affinity, hardness and electrophilicity index of these complexes have also been discussed. The modifications of energy levels and charge density distributions of the frontier orbitals are also analysed. The absorption spectra of these complexes lie in the visible region, which suggests their application in fluorescent-bio imaging. The mechanism of cooperativity effect is studied by molecular orbital potential (MEP), atoms-in-molecules (AIM) and natural bond orbital analyses. Most metalated pairs have smaller HOMO–LUMO band gaps than the isolated mismatch nucleobases which suggest interesting consequences for electron transfer through DNA duplexes.     

Theoretical studies on the structures and absorption spectra of–C n R2n+1(R = H,F; n = 1, 2) substituted 5-(2-pyridyl) pyrazolate boron complexes

The molecular structures, electronic structures and absorption characters of–CH₃,–C₂H₅,–CF₃,–C₂F₅ substituted 5-(2-pyridyl) pyrazolate boron complexes were presented by density functional theory (DFT). The ground state structures of the title complexes were optimised at B3LYP/6-31G* level. In addition, a time dependent density functional theory (TD-DFT) method is applied to investigate the properties of absorption spectra and electronic transition mechanism which were based on the ground state geometries. The results show that the chemical bond formed between nitrogen in the pyridyl ring and boron can be attributed to coordination effect. The boron centre has a typical tetrahedral geometry with the adjacent atoms. The calculated absorption wavelengths for–CF₃,–C₂F₅ substituted 5-(2-pyridyl) pyrazolate boron complexes are in good agreement with the experimental data.     

Modeling of the molecular and electronic structures of multiple-decker sandwich macromolecules with η5-π bonds on the basis of biscyclopentadienyl derivatives 60H10 of a C60 fullerene

The molecular and electronic structures of the (CpFe)₂C₆₀H₁₀ complex of the D _5d symmetry, where Cp is the $^ \cdot C_5 H_5 $ cyclopentadienyl radical, are simulated using the ab initio Hartree-Fock-Roothaan method in the 3–21G basis set. In this complex, hydrogen atoms are attached to carbon atoms of the C₆₀ fullerene which occupy α-positions with respect to two oppositely lying five-membered rings. Each FeCp semisandwich moiety is linked to atoms of one of these five-membered rings by the η⁵-π-type bond. It is found that the energy of the η⁵-π Fe-C₆₀H₁₀ bonds in the (CpFe)₂C₆₀H₁₀ complex is comparable to that of the η⁵-π Fe-Cp bond in the FeCp₂ ferrocene molecule. The optimum geometry calculated for the (CpFe)₂C₆₀H₁₀ complex is used for modeling of the structure of the quasi-linear macromolecule [-FeC₆₀H₁₀-]_n, (I). The band structure of the energy spectrum of macromolecule I is calculated in the valence approximation of the extended Hückel method within the crystalline-orbital approach. The band gap in the spectrum of macromolecule I is ～2.27 eV. The band structure of the spectrum of this macromolecule is compared with the spectra of the hypothetical molecules [-FeCp-]_n and [-FeC₂₀-]_n.     

Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Four novel coordination polymers: Ag(dpa) I, Co(O₃PH)(4,4′-bpy)(H₂O) II, Zn(O₃PH)(4,4′-bpy)_0.5 III and Mn[O₂PH(C₆H₅)]₂(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) ų. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) ų. III crystallizes in monoclinic P21/c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) ų. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) ų. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M^II(O₃PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O₂PH(C₆H₅)]₂ sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag⁺ to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co²⁺ ions, while the original framework remains intact. The removal of 4,4′-bpy in II–IV occurs at elevated temperatures above 250, 200 and 400°C respectively.     

First-principles study on the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn2(H2O)5Mo(CN)7·4H2O (α phase)

First-principles calculations have been performed to study the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn₂(H₂O)₅Mo(CN)₇·4H₂O (α phase).The calculations were based on density-functional theory and the full potential linearized augmented plane wave method (FP-LAPW). The calculated total energies revealed that the compound has a stable ferromagnetic (FM) ground state, which is in agreement with the experiments. The electronic structure of the compound has a half-metallic behavior. The calculated magnetic moment per molecule is about 15.000 μ_B, the magnetic moment are mainly from Mo and Mn atoms with d electronic configuration. It is also found that there exists ferromagnetic interaction between low-spin Mo²⁺ and high-spin Mn³⁺ ions through the Mo-C-N-Mn linear linkages.     

Spectroscopic Studies of Fluorescent Dye <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>′- bis(2-hydroxy-5-methyl-benzylidene)-1,2-ethanediamine and its DNA Complex in Solution

Absorption and fluorescence emission properties of an N-salicylideneamine fluorescent dye molecule N, N-bis(2-hydroxy-5-methylbenzylidene)-1,2-ethanediamine (1) have been studied in three typical solvents—2-methylbutane, ethanol, dimethyl sulphoxide (DMSO), and its DNA complex in methanol/H₂O mixed solvent. The normal absorption band of 1 is observed in both aprotic and protic solvents and has been assigned to the l a transition in the enol form of 1. The long-wavelength absorption band of 1, which is caused by the formation of a cis-keto species in the ground state, is absent in aprotic solvents, but is observable in protic ones. Normal fluorescence emission from the excited enol state of 1 is obtained only when the normal absorption band is excited, while the excited-state intramolecular proton transfer (ESIPT) emissions from both cis- and trans-keto species are recorded in all cases, being acceptable for the variation of the relative emission intensities. A preliminary spectroscopic study of the 1–DNA complex indicates an intercalation-binding mode, the convincing supporting evidence being the enhanced ESIPT fluorescence intensity of 1 when complexed with DNA. Finally, a universal energy-state diagram is given to interpret the experimental results.     

Effect of pressure on the interlayer transport and the electronic structure in the organic quasi-two-dimensional bilayer metal θ-(BETS)<Subscript>4</Subscript>HgBr<Subscript>4</Subscript>(C<Subscript>6</Subscript>H<Subscript>5</Subscript>Cl)

The behavior of the interlayer resistance and the magnetoresistance in the organic quasi-twodimensional bilayer metal θ-(BETS)₄HgBr₄(C₆H₅Cl) is studied at normal pressure and a hydrostatic pressure of 10 kbar. The interlayer transport under atmospheric pressure is found to occur in an incoherent mode. The applied pressure does not change the electronic structure of the conducting layers and causes a transition to a weakly coherent mode at low temperatures.