A promising class of luminescent derivatives of Silver(I) and Gold(I)-N-heterocyclic carbene

Starting from proligand 1-methyl-2-(phenyl)imidazo[1,5-a]pyridine-2-iumchloride ( 1 .HCl), 1-methyl-2-(phenyl)imidazo[1,5-a]pyridine silver(I)chloride, ( 2 ) has been prepared. Synthesis, structures and photophysical properties of (2,2^/−bipyridyl)-1-methyl-2-(phenyl)imidazo[1,5-a]pyridinesilver(I)hexaflurophosphate, ( 3 ), 1-methyl-2-(phenyl)imidazo[1,5-a]pyridinesilver(I)carbazolate, ( 4 ) and 1-methyl-2-(phenyl)imidazo[1,5-a]pyridinegold(I)carbazolate, ( 5 ) are focused. Herein we have first reported the NHC-Ag-(bpy/carbazole). All the complexes have been characterized by elemental analysis, various spectroscopic studies and finally screened for luminescent properties. All the complexes are strongly emissive. Solid state structures of 2 , 3 , 4 and 5 have been determined by X-ray diffraction studies. Conventionally, complex 2 adopts linear geometry whereas complex 3 embraces triangular planar geometry around Ag; complex 4 and 5 clinches linear geometry around Ag/Au. All the complexes absorb light within 275–343 nm. Complex 3 is luminous at ~407 mn, whereas complex 4 and 5 luminous at ~360 nm having short life time 1.00–6.97 ns. The quantum yield (Φ_em) of the complexes varies 0.106–0.186. It is expected variation of luminescence arises due to change of metal and the chromophore (bpy/carbazole). Density Functional Theory (DFT) and Temparature Dependent Density Functional Theory (TDDFT) calculations were performed to verify crystallographically derived parameters and to calculate the UV–Vis properties of the ground state as well as of the first excited state of the complexes.     

Cycloaddition reactions of cyclic ketene-N,S-acetals with 1,2,4,5-tetrazines

Reaction of 3,6-diphenyl-, 3,6-bis(2-pyridyl)- and the unsubstituted 1,2,4,5-tetrazine with 4,5-dihydro-1-methyl-2-(methylthio)pyrrole ( 2 ) and 1-raethyl-2-(methylthio)-4.5,6,7-tetrahydroazepine ( 3 ) gives 4,7-di-R-2,3-dihydro-1-methylpyrrolo[2,3-d]pyridazine ( 4 , R = phenyl, 2-pyridyl, hydrogen) and 6,9-di-R-1-methyl-2,3,4,5-tetrahydropyridazino[4,5-6]azepine ( 5 ), R = phenyl, 2-pyridyl, hydrogen), respectively, in reasonable to good yields. The compounds 4 (R = phenyl, hydrogen) are converted into their corresponding 1-methylpyrrolo-[2,3-d]pyridazines 6 by reaction with potassium permanganate in butanone. Reaction of 3-phenyl-1,2,4,5-te-trazine with 2 and 3 leads to the exclusive formation of the 7-phenyl isomer 4d and 9-phenyl isomer 5d , respectively, indicating that the cycloaddition is regiospecific. The mechanism is discussed.     

Determination of low-level ink photoinitiator residues in packaged milk by solid-phase extraction and LC-ESI/MS/MS using triple-quadrupole mass analyzer

A confirmatory and quantitative method based on liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) has been developed for simultaneous determination of seven photoinitiator residues: benzophenone, (1-hydroxycyclohexyl)phenylketone (Irgacure 184), isopropylthioxanthone (ITX), 2-ethylhexyl-(4-dimethylamino)benzoate (EHA or EHDAB), 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (Irgacure 907), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO) and 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (Irgacure 369) in packaged milk and related packaging materials. Residues of photoinitiators were extracted from milk using acetonitrile, and further enriched and purified on HLB solid-phase extraction cartridges prior to being analyzed by LC-ESI/MS/MS with selected reaction monitoring mode, while photoinitiators in packaging materials were extracted using the same solvent. Satisfactory recovery (from 80 to 111%), intra- and inter-day precision (below 12%), and low limits of quantification (from 0.1 to 5.0 μg kg⁻¹) were evaluated from spiked samples at three concentration levels (5.0, 10.0 and 25.0 μg kg⁻¹ for Irgacure 184 and 2.5, 5.0 and 25.0 μg kg⁻¹ for others). These excellent validation data suggested the possibility of using the LC-ESI/MS/MS method for simultaneous determination of low-level photoinitiator residues migrating from printed food-packaging materials into milk. The method has been successfully applied to the analysis of real samples of different fat contents ranging from 8 to 30 g L⁻¹. The photoinitiator residues were revealed to be higher in milk with higher fat content and the most important contaminations were benzophenone and ITX in concentration ranges of 2.84–18.35 and 0.83–8.87 μg kg⁻¹, respectively.     

Synthesis,nature of electronic transitions,and absorption spectra of the dye based on 4-(methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide

The reaction of 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1Н)-one with pyridine and 4-methylpyridine has afforded the corresponding pyridinium salts. Condensation of 4-methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide with 4-dimethylaminobenzaldehyde has given a new biscyanine dye, 1-{1-[4-(1,2-dihydro-1-methyl-2-oxo-3-quinolinyl)benzoyl]-2-[4-(dimethylamino)-phenyl]ethynyl}-4-{2-[4-(dimethylamino)phenyl]ethynyl}pyridinium bromide. Its electronic spectrum has been analyzed, and quantum-chemical simulation of spatial and electronic structure of its possible isomers has been performed.     

Ultrafast energy transfer between the 3MLCT state of [Ru(II)(dmb)2(bpy-an)]2+ and the covalently appended anthracene

The time scale for triplet-triplet energy transfer (EnT) between a Ru(II) chromophore and a ligand bound anthracene acceptor in [Ru(II)(dmb)2(bpy-an)]2+ (dmb = 4,4'-dimethyl-2,2-bipyridine; bpy-an = 4-(9-anthrylethylene), 4-methyl-2,2-bipyridine) has been measured using femtosecond transient absorption spectroscopy. The appearance of the anthracene excited state is monitored following photoexcitation to a metal-to-ligand charge transfer (MLCT) state via the pi pi* absorption of the triplet excited state of anthracene. Our time-resolved experiments show the presence of fast, sub-100 ps energy transfer to the anthracene occurring on two characteristic time scales of 23 and 72 ps.     

meso‐3,5‐Bis(trifluoromethyl)phenyl‐Substituted Expanded Porphyrins: Synthesis,Characterization, and Optical,Electrochemical, and Photophysical Properties

Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, ¹H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.     

2,4和8-支噁二唑衍生物的三光子吸收和三光子上转换荧光

用飞秒Ti:sapphire激光测定了3个对称噁二唑衍生物4-{N,N-双[4-(4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基)苯基]氨基}苯甲醛(Bis-oxa)、2,5-双{4-[2-N,N-双(4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基}苯基)氨基苯乙烯基]苯基}-1,3,4-噁二唑(Quadri-oxa)和2,5-双(4-{2-N,N-双[({3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}乙烯基)苯基]氨基苯乙烯基}苯基)-1,3,4-噁二唑(Octu-oxa)的三光子吸收谱和三光子荧光光谱. 在1260 nm飞秒激光激发下, 2,4和8-支噁二唑衍生物的三光子吸收系数分别为5.0×10^-5, 10.0×10^-5和10.0×10^-5 cm³/GW², 三光子频率上转换荧光发射波长分别为533, 544和551 nm. 研究了多支化合物线性吸收和透过、单光子荧光及量子产率、荧光寿命、多光子荧光光谱和三光子吸收系数谱. 对称多支噁二唑衍生物具有很强的三光子吸收和上转换荧光性质.     

以N为耦合中心多枝分子的双光子上转换荧光

采用非线性透过率法研究了以N为耦合中心的多枝化合物N-[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N,N-二苯胺(BPODPA), N,N-双[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2-]苯基}-1-乙烯基}苯基}-N-苯胺(BBPOPA)和N,N,N-三[4-{2-(3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}-1-乙烯基}苯基}胺(TBPOA)的双光子吸收性质, 测定了化合物的单光子荧光光谱和双光子上转换荧光光谱, 研究了多枝化对三苯胺分子双光子吸收和双光子激发荧光性质的影响.在800 nm波长的激光激发下,化合物BPODPA、BBPOPA和TBPOA在二氯甲烷溶液中发出很强的蓝绿色双光子上转换荧光, 荧光峰分别位于502、515 和518 nm. 这些多枝结构化合物的双光子吸收截面较大, 双光子吸收增强来源于多枝分子中扩展的π共轭体系和重复单元的协同效应.     

Ethyne-bridged (porphinato)zinc(II)-(porphinato)iron(III) complexes: phenomenological dependence of excited-state dynamics upon (porphinato)iron electronic structure

We report the synthesis, spectroscopy, potentiometric properties, and excited-state dynamical studies of 5-[(10,20-di-((4-ethyl ester)methylene-oxy)phenyl)porphinato]zinc(II)-[5'-[(10',20'- di-((4-ethyl ester)methylene-oxy)phenyl)porphinato]iron(III)-chloride]ethyne (PZn-PFe-Cl), along with a series of related supermolecules ([PZn-PFe-(L)1,2]+ species) that possess a range of metal axial ligation environments (L = pyridine, 4-cyanopyridine, 2,4,6-trimethylpyridine (collidine), and 2,6-dimethylpyridine (2,6-lutidine)). Relevant monomeric [(porphinato)iron-(ligand)1,2]+ ([PFe(L)1,2]+) benchmarks have also been synthesized and fully characterized. Ultrafast pump-probe transient absorption spectroscopic experiments that interrogate the initially prepared electronically excited states of [PFe(L)1,2]+ species bearing nonhindered axial ligands demonstrated subpicosecond-to-picosecond relaxation dynamics to the ground electronic state. Comparative pump-probe transient absorption experiments that interrogate the initially prepared excited states of PZn-PFe-Cl, [PZn-PFe-(py)2]+, [PZn-PFe-(4-CN-py)2]+, [PZn-PFe-(collidine)]+, and [PZn-PFe-(2,6-lutidine)]+ demonstrate that the spectra of all these species are dominated by a broad, intense NIR S1 --> Sn transient absorption manifold. While PZn-PFe-Cl, [PZn-PFe-(py)2]+, and [PZn-PFe-(4-CN-py)2]+ evince subpicosecond and picosecond time-scale relaxation of their respective initially prepared electronically excited states to the ground state, the excited-state dynamics observed for [PZn-PFe-(2,6-lutidine)]+ and [PZn-PFe-(collidine)]+ show fast relaxation to a [PZn+-PFe(II)] charge-separated state having a lifetime of nearly 1 ns. Potentiometric data indicate that while DeltaGCS for [PZn-PFe-(L)1,2]+ species is strongly influenced by the PFe+ ligation state [ligand (DeltaGCS): 4-cyanopyridine (-0.79 eV) < pyridine (-1.04 eV) < collidine (-1.35 eV) < chloride (-1.40 eV); solvent = CH2Cl2], the pump-probe transient absorption dynamical data demonstrate that the nature of the dominant excited-state decay pathway is not correlated with the thermodynamic driving force for photoinduced charge separation, but depends on the ferric ion ligation mode. These data indicate that sterically bulky axial ligands that drive a pentacoordinate PFe center and a weak metal axial ligand interaction serve to sufficiently suppress the normally large magnitude nonradiative decay rate constants characteristic of (porphinato)iron(III) complexes, and thus make electron transfer a competitive excited-state deactivation pathway.     

Synthesis and antifungal activities of a series of (1,2-disubstituted vinyl)imidazoles.

A series of vinylimidazoles containing a hetero atom such as sulfur or oxygen at a beta-position of the vinyl group was prepared and the antifungal activities were tested. It was found that sulfur-substituted derivatives such as (E)-1-[2-(methylthio)-1-[2-(pentyloxy)phenyl]ethenyl]-1H-imidazole (5a-5) and (E)-1-[1-[2-(hexyloxy)phenyl]-2-(methylthio)ethenyl]-1H-imidazole (5a-6) showed excellent antifungal activities against dermatophytes and yeast cells. The stereochemistry of the hydrochloride salt of 5a-5 was determined by X-ray crystallography. The structure-activity relationships were discussed.     

Redox induced reversible structural transformations of dimeric and polymeric phenanthroline-based copper chelates

The synthesis and characterization of copper complexes of the phenanthroline based bridging ligands, 9-methyl-2-(2-[4-[2-(9-methyl-1,10-phenanthrolin-2-yl)ethyl]phenyl]ethyl)-1,10-phenanthroline, 1, and 1,12-bis(9-methyl-1,10-phenanthroline-2-yl)dodecane, 2, are presented. Whereas in the first case a discrete dimeric complex [Cu(2)(1)(2)](BF(4))(2) was formed, in the latter, a coordination polymer [2(Cu(2))(n)](BF(4))(n) resulted. Both of these materials have been characterized by cyclic voltammetry (CV), the electrochemical quartz crystal microbalance (EQCM), and UV-vis spectroscopy and the results compared to those of the monomeric [Cu(dmp)(2)](BF(4)) (dmp is 2,9-dimethyl-1,10-phenanthroline) species. Oxidation of the dimeric species results in its precipitation and reduction results in stripping of the deposited layer as ascertained from CV and EQCM measurements. The electrooxidation of the copper centers in the coordination polymer results in changes in the coordination which are fully reversible upon reduction. The dissociation/regeneration of the coordination polymer as a function of the redox state of the copper centers has been characterized by CV, EQCM, and UV-vis spectroelectrochemistry.     

Photochemical reactions of 7-aminocoumarins. 2. [2 + 2]-cycloadducts with styrene

The photocycloaddition of styrene to 4-methyl-7-aminocoumarin, 4-methyl-7-diethylaminocoumarin, 7-(N-morpholino) coumarin, 3-ethoxycarbonylmethyl-4-methyl-7-diethylaminocoumarin, and coumarin-102 (2,3,6,7-tetrahydro-9-methyl-1H, 5H,11H-[l]-benzopyrano[6,7,8-ij] quinolizin-11-one) was investigated. Adducts of regio- and stereospecific [2 + 2]-cycloaddition to the 3–4 bond were isolated. It was established by means of x-ray diffraction analysis that the phenyl group in the cycloadducts occupies the 1-endo position. The participation of the singlet excited states of the 7-aminocoumarin molecules in [2 + 2]-cycloaddition was demonstrated.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1176–1184, September, 1988.     

Unusual Thermal Rearrangements of N-Cyclohexylidene-4-methyl-1-(methylthio)penta-1,3-dien-1-amine

We have observed unusual thermal rearrangements of N-cyclohexylidene-4-methyl-1-(methylthio)penta-1,3-dien-1-amine to 4,4-dimethyl-2-(methylthio)-3,3a,4,4a,5,6,7,8-octahydrobenzo[4,1]cyclobuta-[1,2-b]pyrrole and 1-cyclohexyl-5-methylpyridine-2(1H)-thione.     

Alkatrienyl Sulfoxides and Sulfones. Part I. 3-Methyl-1,2,4-pentatrienyl Phenyl Sulfoxide-Synthesis and Electrophile-Induced Cyclization Reactions

A method for the synthesis of the 3-methyl-1,2,4-pentatrienyl phenyl sulfoxide 3 by [2,3]-sigmatropic rearrangement of the 3-methyl-1-penten-4-yn-3-yl benzenesulfenate 2 , formed in the reaction of the 3-methyl-1-pentene-4-yn-2-ol 1 with phenylsulfenyl chloride has been created. Possibilities and restrictions of the five-membered heterocyclization in electrophile-induced reactions leading to the synthesis of the 5H-1,2-oxathiol-2-ium salts 5 , 7 , and 8 have been explored. Chlorination of the sulfoxide 2 proceeded with formation of the (E)-2-chloro-3-methylene-1,4-pentadienyl phenyl sulfoxide 4 , while the bromination afforded the 4-bromo-5H-1,2-oxathiol-2-ium bromide 5 , which after reflux in 1,2-dichloroethane eliminated hydrogen bromide and was transformed into the (E)-2-bromo-3-methylene-1,4-pentadienyl phenyl sulfoxide 6 .     

Synthesis and structural characterization of Cu(I) and Ni(II) complexes that contain the bis[2-(diphenylphosphino)phenyl]ether ligand. Novel emission properties for the Cu(I) species

The pseudotetrahedral complexes [Cu(NN)(DPEphos)]BF(4), where DPEphos = bis[2-(diphenylphosphino)phenyl]ether and NN = 1,10-phenanthroline (1), 2,9-dimethyl-1,10-phenanthroline (2), 2,9-di-n-butylphenanthroline (3), or two dimethylcyanamides (4), and NiCl(2)(DPEphos) (5) have been synthesized and structurally characterized by X-ray crystallography and their solution properties examined by use of a combination of cyclic voltammetry, NMR spectroscopy, and electronic absorption spectroscopy. Complexes 1-4 possess a reversible Cu(II)/Cu(I) couple at potentials upward of +1.2 V versus Ag/AgCl. Compounds 1-3 exhibit extraordinary photophysical properties. In room-temperature dichloromethane solution, the charge-transfer excited state of the dmp (dbp) derivative exhibits an emission quantum yield of 0.15 (0.16) and an excited-state lifetime of 14.3 mus (16.1 mus). Coordinating solvents quench the charge-transfer emission to a degree, but the photoexcited dmp complex 2 retains a lifetime of over a microsecond in acetone, methanol, and acetonitrile.     

Triplet excited state in platinum-acetylide oligomers: triplet localization and effects of conformation

An experimental and theoretical investigation was carried out on a series of platinum-acetylide oligomers of the general structure Ph-CC-[PtL2-CC-(1,4-Ph)-CC-]n-PtL2-CC-Ph (where n = 1, 2, 3, 4, 6; Ph = phenyl, 1,4-Ph = 1,4-phenylene; L = P(n-Bu)3, and the geometry at Pt = trans). The objective of this work is to understand the geometry and electronic structure of the ground and triplet excited states of Pt-acetylide oligomers. The experiments carried out include temperature-dependent absorption and photoluminescence spectroscopy (80-298 K range) and ambient temperature transient absorption spectroscopy. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were carried out on several of the oligomers using the hybrid Becke's three-parameter functional with the B3LYP correlation functional and the SDD basis set. The combined experimental and theoretical results provide very clear evidence that the triplet excited state is localized on a chromophore consisting approximately of a single -[PtL2-CC-(1,4-Ph)-CC-PtL2]- repeat unit. DFT calculations indicate that in the ground state conformers that differ in the (rotational) orientation of the 1,4-phenylenes with respect to the plane defined by the PtL2(C)2 units (twisted = t and planar = p) are very close in energy (difference of <1 kcal.mol-1). By contrast, in the triplet excited state, the p conformer is 3 kcal.mol-1 lower in energy than the t conformer. The torsional geometry change in the triplet state is reflected in the low-temperature phosphorescence spectra of the short oligomers, where separate emission bands are seen from the t and p conformers.     

Photochromism of diarylethenes with two nitronyl nitroxides: photoswitching of an intramolecular magnetic interaction

Photochromic diarylethenes that have p-phenylene-substituted benzothiophene aryl groups with and without nitronyl nitroxide radicals at both ends of the molecules were synthesized. The absorption maxima of the closed-ring isomers showed a hypsochromic shift with the increase in the pi-conjugated chain length. The unique behavior was attributed to the stabilization by the resonant quinoid structures. Both photocyclization and photocycloreversion quantum yields of the diarylethene with nitronyl nitroxide radicals were found to increase with the increase in the pi-conjugated chain length. Photoswitching of the magnetic interaction between two nitronyl nitroxide radicals was studied by means of ESR spectroscopy. The change in exchange interaction between open- and closed-ring isomers of 1,2-bis[6-[4-[4-(1-oxyl-3-oxide-4,4,5,5-tetramethylimidazolin-2-yl)phenyl]phenyl]-2-methyl-1-benzothiophen-3-yl]hexafluorocyclopentene was determined to be more than 30-fold.     

Bacteriorhodopsin analogs from diphenylpolyene chromophores

Chromophore-modified bacteriorhodopsin (bR) analogs are prepared, to study the nature of chromophore-protein interaction as well as to develop new bR analogs that can find applications as photoactive element in molecular electronic devices. This article describes the preparation and characterization of hitherto unknown bR analogs based on diphenylpolyene chromophores. Diphenylpolyene compounds, namely, 4-[(E)-2-phenylvinyl]benzaldehyde (1), 3-methyl-5-[4-[(E)-2-phenylvinyl]phenyl]penta-2E,4E-dienal (2), 4-[4-phenylbuta-1E,3E-dienyl]benzaldehyde (3) and 3-methyl-5-[4-[4-phenylbuta-lE,3E-dienyl]phenyl]penta-2E,4E-dienal (4), have been synthesized, and their interaction with bacterioopsin (bOP) has been studied. Whereas aldehydes 2 and 4 interact with bOP and yield bR analogs bR-2 and bR-4, aldehydes 1 and 3 do not yield any pigment. Analogs bR-2 and bR-4 have been characterized for their opsin shift, competitive binding, photochemical properties and fluorescence spectral behavior.     

Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II)

Four structurally related iridium(III) and ruthenium(II) complexes bearing two polar terpyridyl-stilbene derived chromophores 4-(4-{2-[4-(methoxy)phenyl]ethenyl}phenyl)-2,2'-6',2'-terpyridine (ttpyeneanisole) and 4-(4-{2-[phenyl]ethenyl}phenyl)-2,2'-6',2'-terpyridine (tpystilbene) have been synthesised and characterised in the solid state and in solution. In the solid state, the dihedral angle subtending the pyridyl and tolyl groups of 27.1° in the Ir(III) complex [Ir(ttpyeneanisole)(2)]·3PF(6) is more acute than in the Ru(II) derivative [Ru(tpystilbene)(2)]·2PF(6) (35.5°), indicating the presence of a greater degree of π-delocalisation across the terpyridine unit in the former compound. Their luminescence properties in fluid solution have been investigated following both resonant and non-resonant excitation. We have shown that each of the complexes undergoes two-photon excitation when excited in the near infrared (740 to 820 nm), with two-photon absorption cross sections in the range 11-67 × 10(-50) cm(4) s photon(-1). The larger cross sections for the Ir(III) complexes reflect the differences observed in the solid state. This work therefore demonstrates that such complexes are promising as luminescent markers for 3D imaging and illustrates that simple functionalisation of the chromophores and the choice of metal can lead to marked enhancements in the two-photon cross sections (σ(2)) compared to those of simpler heteroleptic polypyridyl based derivatives.     

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes

A series of ruthenium o-phosphane complexes was synthesized and characterized. The reactivity of the prepared complexes was studied by using them as catalysts for the hydroformylation of 1-hexene. The activities depended on the binding mode of the phosphane and on the strength of the ruthenium-phosphane interaction. Strongly coordinated chelating [2-(dimethylamino)phenyl]-(diphenyl) phosphane and [2-(methylthio)phenyl]-(diphenyl) phosphane showed poor activity, while weakly chelated [2-(methoxy)phenyl]-(diphenyl) phosphane and non-chelating phosphanes such as [2-(methyl)phenyl]-(diphenyl) phosphane or [2-(ethyl)phenyl]-(diphenyl) phosphane led to higher activities.