Incorporation of amphiphilic ruthenium(II) ammine complexes into Langmuir-Blodgett thin films with switchable quadratic nonlinear optical behavior

Nine nonlinear optical (NLO) chromophores with pyridinium electron acceptors have been synthesized by complexing new proligands with {Ru(II)(NH(3))(5)}(2+) electron-donor centers. The presence of long alkyl/fluoroalkyl chain substituents imparts amphiphilic properties, and these cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Each complex shows three reversible/quasireversible redox processes; a Ru(III/II) oxidation and two ligand-based reductions. The energies of the intense visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions correlate to some extent with the ligand reduction potentials. (1)H NMR spectroscopy also provides insights into the relative electron-withdrawing strengths of the new ligands. Single crystal X-ray structures have been determined for two of the proligand salts and one complex salt, [Ru(II)(NH(3))(5)(4-C(16)H(33)PhQ(+))]Cl(3)·3.25H(2)O (PhQ(+) = N-phenyl-4,4'-bipyridinium), showing centrosymmetric packing structures in each case. The PF(6)(-) analogue of the latter complex has been used to deposit reproducibly high-quality, multilayered Langmuir-Blodgett (LB) thin films. These films show a strong second harmonic generation (SHG) response from a 1064 nm laser; their MLCT absorbance increases linearly with the number of layers (N) and I(2ω)/I(ω)(2) (I(2ω) = intensity at 532 nm; I(ω) = intensity at 1064 nm) scales quadratically with N, consistent with homogeneous deposition. LB films on indium tin oxide (ITO)-coated glass show electrochemically induced switching of the SHG response, with a decrease in activity of about 50% on Ru(II) → Ru(III) oxidation. This effect is reversible, but reproducible over only a few cycles before the signal from the Ru(II) species diminishes. This work extrapolates our original solution studies (Coe, B. J. et al. Angew. Chem., Int. Ed.1999, 38, 366) to the first demonstration of redox-switching of NLO activity in a molecular material.     

Two-dimensional, pyrazine-based nonlinear optical chromophores with ruthenium(II) ammine electron donors

Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru(II)(NH(3))(5)}(2+) or trans-{Ru(II)(NH(3))(4)(py)}(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru(II) centers from one to two, but remain at constant energy. One or two Ru(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant "off-diagonal" β(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β(0). Both the HRS and the Stark-derived β(0) values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru(II) ammine complexes reported previously.     

Study of nonlinear optical properties of multilayer Langmuir-Blodgett films containing bacteriorhodopsin

Multilayer oriented Langmuir-Blodgett films of bacteriorhodopsin were prepared and their nonlinear optical properties, including second harmonic generation and photoresponse at a two phase-modulated beams mixing, were investigated. The nonlinear component of refractive index of the films was measured.     

Molecularly organized Langmuir-Blodgett films from a ruthenium biphosphine complex

Langmuir-Blodgett (LB) films from a ruthenium complex mer-[RuCl3 (dppb)(4-Mepy)] (dppb = PPh2 (CH2)4PPh2; 4-Mepy = 4-methylpyridine), termed Ru-Pic, display a distinct color, which is different from the coloration exhibited by cast films or chloroform solutions. The solution and cast films are red, while the LB films are green-bluish. The manifestation of the blue color in the LB film finds its explanation in a unique absorption band at 690 nm, which is associated with the oxidation of the phosphine moieties. Fluorescence emission and absorption-reflection infrared spectroscopy measurements revealed the molecular organization in the LB films. In contrast, cast films showed a random distribution of complexes. Surface-enhanced Raman scattering was also used in an attempt to identify the main interactions in Ru-Pic.     

Contrasting linear and quadratic nonlinear optical behavior of dipolar pyridinium chromophores with 4-(dimethylamino)phenyl or ruthenium(II) ammine electron donor groups

In this article, we contrast the optical properties of dipolar chromophores having 4-(dimethylamino)phenyl electron donor (D) and pyridinium acceptor (A) groups with those of closely related cations having pyridyl-coordinated Ru(II) donors. A range of physical data, including that from Stark (electroabsorption) spectroscopy, permits unprecedented quantitative comparisons, most notably regarding the effects of extension of bridging polyene chains. The purely organic compounds display normal optical properties in that their intense, visible pi --> pi intramolecular charge-transfer (ICT) bands red-shift as the number of E-ethylene units (n) increases from 1 to 3 and the associated static first hyperpolarizabilities beta(0) increase steadily with n. The related Ru(II) complexes show intense, visible d --> pi metal-to-ligand charge-transfer (MLCT) bands, which are found to lower energy when compared with the ICT transitions of the corresponding organics. Abnormally, these MLCT bands blue-shift as n increases, and beta(0) maximizes at n = 2. Time-dependent density-functional theory and finite field calculations verify these empirical trends for both types of compound, which can be rationalized as arising from the differing orbital structures of the chromophores and the associated degrees of D-A electronic coupling.     

Langmuir-Blodgett films of a clay mineral and ruthenium(II) complexes with a noncentrosymmetric structure

Mono- and multilayers of amphiphilic [Ru(phen)(2)(dcC12bpy)](2+) (phen = 1,10-phenanthroline, dcC12bpy = 4,4'-caboxyl-2,2'-bipyridyl didodecyl ester) hybridized with a clay mineral have been prepared by a modified Langmuir-Blodgett method, and their structures and properties have been investigated. Formation of a hybrid monolayer of the Ru(II) complex cations and the clay platelets at an air-clay suspension interface was confirmed by surface pressure-molecular area (pi-A) isotherm measurement and atomic force microscopic (AFM) observation. Multilayers were fabricated by depositing the hybrid monolayers onto glass substrates. The absorbance at 492 nm due to the Ru(II) complex cation in the multilayer increased linearly with the increase in the layer number, indicating layer-by-layer deposition of the hybrid monolayers. Because no increase in the second-harmonic generation (SHG) signal from the multilayers against the layer number was observed, the orientation of the Ru(II) complex cations in the layer would be disturbed. The hydrophilic surface of the transferred hybrid monolayer can be converted to a hydrophobic surface by dipping it in an aqueous solution of octadecylammonium chloride (ODAH(+)Cl(-)). The multilayers modified with ODAH(+) showed a quadratic relation between the SHG intensity and the layer number. This means that the Ru(II) complex cations in the multilayer are successfully oriented in a noncentrosymmetric way by the conversion of the surface property. Both a racemic mixture and an enantiomer of the Ru(II) complex cations were employed to examine the chiral effect on the film properties. The chiral contribution to the SHG signal was enhanced in the multilayer modified with ODAH(+).     

Directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate)

We have demonstrated directional photoinduced electron transfer in paraquat silicate thin films containing entrapped ruthenium(II)-tris(bathophenanthroline-disulfonate (RuBPS). The films were made by electrochemically-induced hydrolysis of a silane analogue of paraquat with ruthenium(II)-tris(bathophenanthroline-disulfonate as its ion pair.     

Highly unusual effects of pi-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes

We have used several techniques, including hyper-Rayleigh scattering and Stark spectroscopy, to investigate the effects of polyene chain length on the optical properties of complexes containing ruthenium(II) electron donor groups and pyridinium electron acceptors. In marked contrast with all other known donor-acceptor polyenes, conjugation extension beyond a single double bond in the dipolar complexes studied leads to blue-shifting of the intramolecular charge-transfer absorptions. Furthermore, the static first hyperpolarizabilities beta0 become maximized with trans-1,3-butadienyl linkages and then decrease in complexes with three CH=CH bonds. Our results clearly demonstrate that the molecular engineering criteria for metal-containing nonlinear optical chromophores can differ dramatically from those for purely organic compounds.     

Studies of Langmuir-Blodgett films of an ion pair metal complex containing Eu(III)-Ru(II) dual chromophores

A surfactant ion-pair complex, [Ru(bpy)(2)L][Eu(NTA)(4)](2) (in which L = 1-docosyl-2-(2- pyridyl)benzimidazole, bpy = 2,2'-bipyridine, and NTA = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionato) has been synthesized. The surface pressure-area isotherm measurements show that the complex forms a stable Langmuir film at the air-water interface without adding any electrolytes into the subphase. The monolayers formed at the surface pressures of 5 mN m(-1) and 20 mN m(-1), have been successfully transferred onto glass and quartz substrates with the transfer ratios close to unity. The Langmuir-Blodgett films were studied by UV-visible, infrared, and emission spectroscopies, atomic force microscopy, and cyclic voltammetry. The optical, redox, and morphology properties of the LB films were found to be significantly affected by the target surface pressures used for the film depositions.     

Quinoxaline-based conjugated polymers containing ruthenium(II) bipyridine metal complex

A series of novel quinoxaline-based conjugated polymers which contain a ruthenium(II) bipyridine complex were synthesized by the Suzuki coupling reactions. UV/VIS spectroscopy showed that the spectral features of the polymers are dependent on the amount of metal complex present. Results from excitation and emission spectroscopy suggest an energy transfer between the backbone and the metal complex. The polymers exhibit hole carrier mobilities of ≈ 10⁻⁵ cm² · V⁻¹ · s⁻¹, which is comparable to organic photoconductors.     

Mechanistic insights into photochromic behavior of a ruthenium(II)-pterin complex

The pterin‐coordinated ruthenium complex, [Ru^II(dmdmp)(tpa)]⁺ ( 1 ) (Hdmdmp=N,N‐dimethyl‐6,7‐dimethylpterin, tpa=tris(2‐pyridylmethyl)amine), undergoes photochromic isomerization efficiently. The isomeric complex ( 2 ) was fully characterized to reveal an apparent 180° pseudorotation of the pterin ligand. Photoirradiation to the solution of 1 in acetone with incident light at 460 nm resulted in dissociation of one pyridylmethyl arm of the tpa ligand from the Ru^II center to give an intermediate complex, [Ru(dmdmp)(tpa)(acetone)]²⁺ ( I ), accompanied by structural change and the coordination of a solvent molecule to occupy the vacant site. The quantum yield (?) of this photoreaction was determined to be 0.87 %. The subsequent thermal process from intermediate I affords an isomeric complex 2 , as a result of the rotation of the dmdmp^2? ligand and the recoordination of the pyridyl group through structural change. The thermal process obeyed first‐order kinetics, and the rate constant at 298 K was determined to be 5.83×10^?5 s^?1. The activation parameters were determined to be ΔH^≠=81.8 kJ mol^?1 and ΔS^≠=?49.8 J mol^?1 K^?1. The negative ΔS^≠ value indicates that this reaction involves a seven‐coordinate complex in the transition state (i.e., an interchange associative mechanism). The most unique point of this reaction is that the recoordination of the photodissociated pyridylmethyl group occurs only from the direction to give isomer 2 , without going back to starting complex 1 , and thus the reaction proceeds with 100 % conversion efficiency. Upon heating a solution of 2 in acetonitrile, isomer 2 turned back into starting complex 1 . The backward reaction is highly dependent on the solvent: isomer 2 is quite stable and hard to return to 1 in acetone; however, 2 was converted to 1 smoothly by heating in acetonitrile. The activation parameters for the first‐order process in acetonitrile were determined to be ΔH^≠=59.2 kJ mol^?1 and ΔS^≠=?147.4 kJ mol^?1 K^?1. The largely negative ΔS^≠ value suggests the involvement of a seven‐coordinate species with the strongly coordinated acetonitrile molecule in the transition state. Thus, the strength of the coordination of the solvent molecule to the Ru^II center is a determinant factor in the photoisomerization of the Ru^II–pterin complex.     

Electrochemical behavior of complex based on ruthenium(II) phthalocyaninate

The electrochemical reactions of ruthenium(II) bis(triethylenediamine)tetra-tret-butyl-phthalocyaninate in dimethylformamide are studied. Two reversible redox reactions on the platinum amalgam electrode are revealed at the potentials of ?0.73 and ?1.16 V (Ag/AgCl). Similarly to several other phthalocyanines, these redox reactions correspond to the successive transfer of two electrons to phthalocyanine ring. A new phenomenon, which has not been reported in the literature for phthalocyanines, namely, the cathodic polymerization, is discovered. Thus formed polymer is redox-active, and only one cathodic reaction at the potentials from ?0.78 to ?0.84 V (a shift in the cathodic direction takes place as the film thickness increases) is observed in the polymer. In addition, the polymer exhibits also considerable electron conductivity that enables one to perform various electrochemical reactions in a wide potential range on the electrode modified with the polymer.     

Photophysical and electrochemical behavior of thin solid films based on a three-dimensional ruthenium complex network

RuL ₃ ²⁺ (L=2,2′-bipyridine-4,4′-diphosphonic acid) thin solid films were fabricated by three-dimensional linking between the phosphonic acid substituents of L and Zr(O)Cl₂. The RuL₃ chromophores in the films are electronically independent of each other in the ground state and give emission spectra essentially identical to that of RuL ₃ ²⁺ in solution, although the emission lifetime is much shorter. The films are electrochemically active, showing pseudo-reversible oxidation behavior in cyclic voltammetry. A preliminary attempt has been made to apply these films to photoelectrochemical cells.     

Syntheses and spectroscopic and quadratic nonlinear optical properties of extended dipolar complexes with ruthenium(II) ammine electron donor and N-methylpyridinium acceptor groups

In this paper, we describe the extremely unusual optical properties of Ru(II)-based electron donor-acceptor (D-A) polyene and some closely related chromophores. For three different polyene series, the intense, visible d-->pi* metal-to-ligand charge-transfer bands unexpectedly blue-shift as the number of E-ethylene units (n) increases from 1 to 3, and the static first hyperpolarizabilities beta(0) determined via hyper-Rayleigh scattering and Stark spectroscopy maximize at n = 2, in marked contrast to other known D-A polyenes in which beta(0) increases steadily with n. Time-dependent density-functional theory and finite field calculations verify these empirical trends, which arise from the orbital structures of the complexes. This study illustrates that transition metal-based nonlinear optical chromophores can show very different behavior when compared with their more thoroughly studied purely organic counterparts.     

Third-order nonlinear optical response of a new polymeric material based on epoxides containing a nickel(II) complex

A novel polymeric material having nonlinear optical properties has been prepared from the diglycidyl ether of bisphenol A and a macrocyclic complex of nickel(II). It has been shown that relatively high levels of third-order nonlinear susceptibility of polymers can be obtained without the use of highly conjugated systems. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Nauka Prospect, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 3, pp. 165–169, May–June, 1997.     

Quadratic nonlinear optical properties of ruthenium (II)-bipyridine complexes in crystalline powders

Quadratic nonlinear optical properties for the crystalline powders of two types of ruthenium-bipyridine [Ru(bipy)₃] complexes were investigated. The nonlinear optical processes markedly depended on the molecular structures of the ruthenium complexes. Second harmonic generation (SHG) and very weak two-photon emission were observed for the alkylated ruthenium-bipyridine compexes with two long alkyl chains attached via amide bonds (RuC_nB), whereas only two-photon emission was observed for Ru(bipy)₃. The existence of two amide bonds in one bipyridine ligand for RuC_nB complexes most probably enhanced the molecular hyperpolarizability as compared with Ru(bipy)₃. The SHG intensity from RuC_nB complexes increased in the order RuC₁₈B < RuC₁₂B < RuC₁₆B. The order of SHG intensity from RuC_nB was ascribed to the difference in size of each crystalline powder estimated by X-ray diffraction methods.     

Luminescent properties of tris(2,2'-bipyridine)ruthenium(II) in sol-gel-processed dip-coated thin films

The luminescence decay and spectral behavior of ruthenium(II)-tris-1,2-bipyridine dichloride dissolved in different organically modified silicate gel matrixes were investigated. Dip-coated thin films were synthesized from tetraethoxysilane (TEOS), methyltriethoxysilane (MTEOS), ethyltriethoxysilane (ETEOS), and methyl- trimethoxysilane (MTMOS). A blue shift in the ruthenium complex emission spectrum with respect to the aqueous solution was observed for all the films on the sol to gel conversion. This spectral shift was slightly dependent on the precursor used to obtain the films and independent of the reaction pH to prepare the "sol". In the data treatment of the time-resolved luminescence measurements, it was assumed that the distribution of the luminophore in the films was nonhomogeneous. The analysis of the luminescence decay profiles was based on a multisite model. All decay curves are best described by a double-exponential model. The parameters of the decay components depended principally on the thermal treatment used in the processing of the films. The lifetimes decreased and the emission espectra showed a red shift with the increase in the drying temperature. A luminescence quenching of the ruthenium complex in the films by dissolved oxygen in aqueous solution was also observed. The quenching rate constant obtained from the preexponential amplitude-weighted mean lifetimes (tau(M)) was in the order of 10(9) M(-1) s(-1). When a phenolic derivative was used as quencher the process rate was greatly reduced compared to the quenching in water. It would seem that the metallic complex sequestered within the film is placed either into a higher microviscosity microenvironment or in a location which the phenolic quencher cannot access. In both cases, the quenching plot based on tau(o)(M)/tau(M) could be fitted satisfactorily by a sum of two terms of Stern-Volmer. This fact is indicative of the matrix microheterogeneity for the films and is fully consistent with the biexponential nature of the luminescence intensity decay profiles.     

Three-dimensional nonlinear optical chromophores based on metal-to-ligand charge-transfer from ruthenium(II) or iron(II) centers

In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' '-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D(3) chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.