Synthesis,Characterization, and Antimicrobial Activity of Silver(I) and Copper(II) Complexes of Phosphate Derivatives of Pyridine And Benzimidazole

Two silver(I) complexes—{[Ag(4‐pmOpe)]NO₃}_n and [Ag(2‐bimOpe)₂]NO₃—and three copper(II) complexes—[Cu₄Cl₆O(2‐bimOpe)₄], [CuCl₂(4‐pmOpe)₂], and [CuCl₂(2‐bis(pm)Ope]—were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin‐4‐ylmethyl)phosphate (4‐pmOpe), 1H‐benzimidazol‐2‐ylmethyl diethyl phosphate (2‐bimOpe), and ethyl bis(pyridin‐2‐ylmethyl)phosphate (2‐bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4‐pmOpe)]NO₃}_n and [Cu₄Cl₆O(2‐bimOpe)₄] were determined by single‐crystal X‐ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ～19 μM ). [Ag(2‐bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin‐resistant Staphylococcus epidermidis, with MIC values of ～5 and ～10 μM , respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL^?1.     

Sulfur bridging by acetophenone thiosemicarbazone in [Ag(μ-dppm)2(μ-SR)Ag(ONO2)](NO3) dimer with a new {Ag2(μ-P,P)2(μ-SR)} core

Acetophenone thiosemicarbazone (Haptsc) with silver(I) nitrate and Ph₂P–CH₂–PPh₂ (dppm) has formed a first example of triply hetero-bridged [Ag(μ-P,P-dppm)₂(μ-S-Haptsc)Ag(ONO₂)]NO₃ dimer with a short Ag⋯Ag contact of 2.9939(7) Å.     

A Novel Precursor for Preparation of Silver Nanoparticles: Synthesis, Characterization and Crystal Structure of Ag(PPh3)2(2-pyCOO)

A novel silver complex, Ag(PPh₃)₂(2-pyCOO)·0.5H₂O·0.5C₂H₆O, was prepared from Ag(CH₃COO)(PPh₃)₂ and 2-pyridinecarboxylic acid and after characterization by elemental analysis, infrared, ¹H and ³¹P NMR spectroscopes, and X-ray crystallography, was used as a precursor for the preparation of silver nanoparticles. The silver nanoparticles were obtained by thermolysis of the silver complex at 350 °C in the presence of oleic acid as a surfactant. Resulting silver nanoparticles were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The formation of silver nanoparticles with an average size of 60 nm and spherical morphology was confirmed by SEM. Bulk silver particles were obtained instead of silver nanoparticles when thermolysis of the silver complex was carried out in the absence of oleic acid.     

Photoluminescence of Cu(I)(PPh3)2(8-quinolinolate)

The complex Cu(I)(PPh₃)₂(oxinate) with oxine = 8-quinolinole is luminescent under ambient conditions. In the solid state it shows an emission which originates from the lowest-energy oxinate ILCT state. It consists of a fluorescence and a phosphorescence. In solution saturated with argon, a single broad emission band appears which seems to be composed of a more intense fluorescence and a much weaker phosphorescence at longer wavelength. If this solution is saturated with air, the complete emission band becomes less intense. This is quite surprising, since the oxinate ILCT fluorescence of other oxinate complexes is not quenched by oxygen. It is conceivable that the fluorescence largely consists of a delayed fluorescence. When the emitting triplet is depopulated by a thermally activated transition to the fluorescent singlet, both emissions, the delayed fluorescence and the phosphorescence, may undergo a luminescence quenching. For a simple comparison, the photoluminescence of Ag(PPh₃)₂(oxinate) was also briefly examined. The absorption and emission spectra of this silver complex in solution at r.t. resemble those of the copper complex.     

A Fluorescent Silver(I) Carbene Complex with Anticancer Properties: Synthesis,Characterization, and Biological Studies

The silver(I) N-heterocyclic carbene (NHC) complex bis(1-(anthracen-9-ylmethyl)-3-ethylimidazol-2-ylidene) silver chloride ([Ag(EIA)₂]Cl), bearing two anthracenyl fluorescent probes, has been synthesized and characterized. [Ag(EIA)₂]Cl is stable in organic solvents and under physiological conditions, and shows potent cytotoxic effects in vitro toward human SH-SY5Y neuroblastoma cells. The interactions of [Ag(EIA)₂]Cl with a few model biological targets have been studied as well as its ability to be internalized in cells. The in vitro anticancer activity is apparently related to the level of drug internalization. Notably, [Ag(EIA)₂]Cl does not react with a few model proteins, but is capable of binding the C-terminal dodecapeptide of thioredoxin reductase hTrxR(488–499) and to strongly inhibit the activity of this enzyme. Binding occurs through an unconventional process leading to covalent binding of one or two carbene ligands to the C-terminal dodecapeptide with concomitant release of the silver cation. To the best of our knowledge, this mode of interaction is reported here for the first time for Ag(NHC)₂ complexes.     

Formation of double-surface-silvered polyimide films via a direct ion-exchange self-metallization technique: The case of BPADA/ODA and [Ag(NH3)2]+

Double-surface-silvered polyimide (PI) films have been successfully fabricated via a direct ion-exchange self-metallization method using silver ammonia complex cation ([Ag(NH₃)₂]⁺) as silver resource and bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride/4,4′-oxydianiline (BPADA/ODA)-based poly(amic acid) (PAA) as the PI precursor. The alkaline characteristic of the silver precursor dramatically improves the efficiency of the ion exchange and film metallization process. By using an aqueous [Ag(NH₃)₂]⁺ solution with a concentration of only 0.01M and an ion-exchange time of only 5 min, metallized films with desirable performance could be easily obtained by simply heating the silver(I)-doped PAA films to 300°C. The strong hydrolysis effect of the basic [Ag(NH₃)₂]⁺ cations on the flexible and acidic BPADA/ODA PAA chains was observed during the ion exchange process by the quantitative evaluation of the mass loss of PAA matrix. Nevertheless, under the present experimental conditions, the final metallized film essentially retained the basic structural, thermal, and mechanical properties of the pristine PI, which make it a truly applicable material. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

The quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (M_n) and narrow molecular weight distribution (M_w/M_n) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry     

Synthesis,Spectroscopy, Single-Crystal Structure Analysis and Antibacterial Activity of Two Novel Complexes of Silver(I) with Miconazole Drug

In a previous article, we reported on the higher toxicity of silver(I) complexes of miconazole [Ag(MCZ)₂NO₃ (1)] and [Ag(MCZ)₂ClO₄ (2)] in HepG2 tumor cells compared to the corresponding salts of silver, miconazole and cisplatin. Here, we present the synthesis of two silver(I) complexes of miconazole containing two new counter ions in the form of Ag(MCZ)₂X (MCZ = 1-[2-(2,4-dichlorobenzyloxy)-2-(2,4-dichlorophenyl)ethyl]-1H-imidazole]; X = BF₄⁻ (3), SbF₆⁻ (4)). The novel silver(I) complexes were characterized by elemental analysis, ¹H NMR, ¹³C NMR and infrared (IR) spectroscopy, electrospray ionization (ESI)-MS spectrometry and X-ray-crystallography. In the present study, the antimicrobial activity of all obtained silver(I) complexes of miconazole against six strains of Gram-positive bacteria, five strains of Gram-negative bacteria and yeasts was evaluated. The results were compared with those of a silver sulfadiazine drug, the corresponding silver salts and the free ligand. Silver(I) complexes exhibited significant activity against Gram-positive bacteria, which was much better than that of silver sulfadiazine and silver salts. The highest antimicrobial activity was observed for the complex containing the nitrate counter ion. All Ag(I) complexes of miconazole resulted in much better inhibition of yeast growth than silver sulfadiazine, silver salts and miconazole. Moreover, the synthesized silver(I) complexes showed good or moderate activity against Gram-negative bacteria compared to the free ligand.     

Palladium‐Catalyzed Synthesis of (Z)‐3‐Arylthioacrylic Acids and Thiochromenones

The three‐component reaction of aryl halides, sodium sulfide pentahydrate (Na₂S⋅5 H₂O), and propiolic acid in the presence of 2.5% bis(triphenylphosphine)palladium chloride [Pd(PPh₃)₂Cl₂], 5% 1,4‐bis(diphenylphosphino)butane (dppb) and 2 equivalents of 1,8‐diazabicycloundec‐7‐ene (DBU) produces stereoselectively (Z)‐3‐arylthioacrylic acids in good yields. A study of the reaction pathway suggested that the C S bond formation between aryl halides and Na₂S⋅5 H₂O proceeded first, and the resulting intermediate reacted with propiolic acid to produce the desired product. In addition, when the resulting product was treated with acid, the respective thiochromenones were formed in good yields.     

Solvent extraction of silver(I) from nitrate media using thiourea derivatives

Liquid–liquid extraction of Ag(I) from nitrate solutions using N‐(N′,N′‐diethyl thiocarbamoyl)‐N″‐phenylbenzamidine (TCBA) and 1‐6,‐diethylcarbamoyl imino‐1,6‐diphenyl‐2,5 dithiahexane (TCTH) dissolved in cumene has been studied. The extraction of Ag(I) from 1 mol dm⁻³ NO₃⁻ solutions by TCTH and TCBA was investigated as a function of several variables: equilibration time, organic phase diluent, pH of aqueous phase, Ag(I) and NO₃⁻ concentration in aqueous phase as well as TCBA and TCTH concentrations. Experimental equilibrium data were analysed numerically using the programs LETAGROP‐DISTR and LETAPL and the results showed that Ag(I) extraction could be explained assuming the formation of AgL and AgNO₃HL with TCBA (HL) and AgNO₃S with TCTH (S). The metal extraction was not influenced significantly by the structures of the thiourea derivatives used as extractants. The back extraction of Ag(I) from loaded organic phase was performed using different strippants and 0.5 mol dm⁻³ NaSCN was found to be efficient for this purpose. © 2000 Society of Chemical Industry     

Amphiphilic poly(acrylonitrile‐co‐acrylic acid)/silver nanocomposite additives for the preparation of antibiofouling membranes with improved properties

This work focuses the preparation of polymer‐silver nanocomposite (Ag‐Nc) dense free standing films and nonwoven fabric supported porous ultrafiltration membranes with improved membrane performance and long‐term antibiofouling properties. New polyacrylonitrle‐based Ag‐Ncs, poly(acrylonitrle‐co‐acrylic acid)‐silver (PAN‐co‐PAA‐Ag) containing 35 wt% of PAA and 0.35–0.65 wt% of Ag‐nanoparticles (Nps) were synthesized and used as additives for the fabrication of PAN‐based (PAN/PAN‐co‐PAA‐Ag) Ag‐Nc porous membranes and dense‐free standing films. The Ag‐Nps were homogeneously dispersed into the PAN‐co‐PAA random copolymer matrix. The prepared membranes (PAN/PAN‐co‐PAA‐Ag) showed combination of properties such as excellent antimicrobial activity towards both Gram Negative and Gram Positive bacteria (prevent biofilm formation), improved protein antifouling properties, and enhanced water flux when compared to neat PAN‐based membrane. The antimicrobial properties, hydrophilicity, and the water flux of various membranes follow the following order for the membranes PAN < PAN/PAN‐co‐PAA < PAN/PAN‐co‐PAA‐Ag. Extraneous addition of small amount of polyethylene glycol (PEG) during preparation of additive i.e. [PEG + PAN‐co‐PAA]‐Ag further improved the protein antifouling properties of the PAN‐based membranes (PAN/[PEG+PAN‐co‐PAA‐Ag]). The dispersed Ag‐Nps were stable on the surface of phase inverted membranes for long period of time and PAN/PAN‐co‐PAA‐Ag membranes are therefore suitable for long‐term water treatment under bacterial environment. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Reusable Gold(I) Catalysts with Unique Regioselectivity for Intermolecular Hydroamination of Alkynes

Two gold(I) phosphine complexes bearing the low‐coordinating bis(trifluoromethanesulfonyl)imidate ligand, namely AuSPhosNTf₂ and AuPPh₃NTf₂, are active catalysts for the regioselective intermolecular hydroamination of both internal and terminal alkynes under mild reaction conditions. The catalysts show a regioselectivity based on electronic rather than steric factors, which allow the preferential synthesis of regioisomers opposite to those described previously. This subtle chemo‐ and regioselectivity depends on the catalyst, substrates and reaction conditions employed, and allows one to perform new tandem reactions. These gold(I) complexes operate under free‐solvent conditions, without exclusion of air, without addition of acidic promoters and can be quantitatively recovered and reused by simple precipitation in hexane.     

Controlled free radical photopolymerization of styrene initiated by trithiocarbonate

Density functional theory calculations are reported for prediction of the trends in C S bond dissociation energies and atomic spin densities for radicals using S,S′‐bis(α,α′‐dimethyl‐α‐acetic acid) trithiocarbonate (TTCA) and bis(2‐oxo‐2‐phenylethyl) trithiocarbonate (TTCB) as reversible addition fragmentation chain transfer (RAFT) reagents. The calculations predict that the value of the C S bond length (1.865 Å) of TTCA is longer than that (1.826 Å) of TTCB, and TTCA is more effective for the polymerization of styrene (St) compared to TTCB as predicted by density functional theory. In photopolymerizations, pseudo‐first‐order kinetics were confirmed for TTCB‐mediated photopolymerization of St due to the linear increase of ln([M]₀/[M]) up to about 28% conversion, suggesting the living characteristics behavior of the photopolymerization of St in the presence of TTCB. For both TTCA and TTCB the polydispersities change with increasing conversion in the range 1.10–1.45, typical for RAFT‐prepared (co)polymers and well below the theoretical lower limit of 1.50 for a normal free radical polymerization. In addition, the triblock copolymer polystyrene‐block‐poly(butyl acrylate)‐block‐polystyrene (PS PBA PS) was successfully prepared, with very good control over molecular weight and narrow polydispersity (M_w/M_n = 1.45), using PS S C(S) S PS as macro‐photoinitiator under UV irradiation at room temperature. This indicated that this reversible and valid strategy led to a better controlled block copolymer with defined structures. Copyright © 2007 Society of Chemical Industry     

The Mutual Effect of Iron(III) and Silver(I) Species in Concentrated Chloride Medium

Abstract

Earlier studies carried out to evaluate the selectivity of solvating extractants towards silver(I) in concentrated chloride media revealed that an intriguing situation occurs if a given excess of iron(III) concentration is present in the aqueous solution: the extraction of silver(I) becomes almost quantitative and independent of the initial chloride content. On the assumption that this effect may be due to a phenomenon occurring in the aqueous phase, a systematic study involving solutions containing different Ag(I), Fe(III), and HCl concentrations was carried out by solvent extraction and capillary electrophoresis. Capillary electrophoresis suggests that the AgCl₃ ^2? amount in solution decreases in the presence of Fe(III), whereas FeCl₃ seems to be partially converted onto FeCl₄ ^?. From the experiments performed, it can be concluded that the presence of Fe(III) seems to facilitate the formation of less anionic Ag(I) species, which are in turn more easily extracted by solvating extractants. Furthermore, the presence of FeCl₄ ^? has been detected in the organic phase of triisobutylphosphine sulfide (TIBPS) by UV‐Vis spectrophotometry, after equilibration with HCl solutions containing both Ag(I) and Fe(III), which was not identified during similar experiments carried out in the absence of Ag(I). Speciation of silver(I) and iron(III) in concentrated chloride medium has also been worked out by a numerical methodology.     

Formation of poly(methyl methacrylate) with novel solubility characters in the photopolymerization with bis(cyclopentadienyl)titanium dichloride in a water–methanol mixture

Methyl methacrylate (MMA) was observed to be easily polymerized in the photopolymerization with bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) in a water–methanol mixture under irradiation of a 15-W fluorescent room lamp. The polymerization proceeded heterogeneously. The rate (R_p) of heterogeneous photopolymerization in a 1 : 1 (v/v) water–methanol mixture at 40°C was apparently given by R_p=k[Cp₂TiCl₂]^0.2 [MMA]^2.4. The resulting poly(MMA) was found to contain a tetrahydrofuran (THF)-insoluble part. The separated THF-insoluble part differed significantly from the usual radical poly(MMA) in solubility characters. It is of great interest that the THF-insoluble poly(MMA) was soluble in benzene and toluene, but insoluble in polar solvents, such as ethyl acetate, acetone, methyl ethyl ketone, dimethylformamide, and dimethylsulfoxide. The copolymerization results of MMA and acrylonitrile revealed that the present photopolymerization initiated with Cp₂TiCl₂ proceeds via a radical mechanism. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 525–531, 1998     

Monomers for adhesive polymers, 8a crosslinking polymerization of selected N‐substituted bis(acrylamide)s for dental filling materials

The free‐radical polymerization of bis‐(N‐ethylacrylamido)‐ethylenglycol ( I ), N,N′‐dimethyl‐1,6‐bis (acrylamido)‐hexan ( II ), and N,N′‐diethyl‐1,3‐bis(acrylamido)‐propan ( III ) were investigated. The cross‐linking polymerization was followed in bulk by using the ampoules technique and gravimetry. Polymerizations exhibited an abnormal kinetic behavior. For the monomer II , for example, the reaction order to 2,2′‐ azobisisobutyronitril (AIBN) initiator of 1.28, and the polymerization overall activation energy of 151 kJ/mol between 50 and 75°C were determined. The increasing temperature and decreasing initiator concentration resulted in an increase of double bonds consumption in the formed polymer network. At 75°C the residual unsaturation was under 2%, compared with 9.9% at 50°C. The monomer conversion‐time dependences were complemented also with differential scanning calorimetry (DSC) recording the heat released during polymerization. The extension of peak time with decreasing the instant heat flow rate at this point sort the studied bis(acrylamide)s according the reactivity in the following sequence: monomer III > I > II . The polymer samples sol–gel analyses in ethanol allowed the determination of the molecular weight M_c between the network crosslinks. The presence of microgel particles at the very beginning of polymerization and the changes in chain conformation with temperature we consider as the way in which was affected the polymerization kinetics of these monomers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pyridin‐, Quinolin‐ and Acridinylidene Palladium Carbene Complexes as Highly Efficient C–C Coupling Catalysts

A series of four new complexes bearing N‐heterocyclic carbene ligands (NHCs) as well as four compounds bearing N‐heterocyclic carbene ligands with remote heteroatoms (rNHCs) of the general types [(NHC)(PPh₃)₂PdCl]⁺BF₄⁻ and [(rNHC)(PPh₃)₂PdCl]⁺BF₄⁻, respectively, have been prepared in high yields. Crystal and molecular structures have been determined for four representative examples. These compounds proved to be efficient catalysts for aryl coupling reactions of the Heck and Suzuki types (reaching TONs of as high as 6,200,000). Both aryl bromides and aryl chlorides can be used as substrates. Like the well known mixed, standard (NHC)(phosphine) compounds, the new six‐numbered, one‐N‐heterocyclic carbene complexes (and in particular certain rNHC‐containing ones) also combine the advantageous stability of bis(carbene) and the high activity of bis(phosphine) complexes. Furthermore, their good catalytic performance and, especially, their easy synthesis based on cheap and commercially available starting materials, make them by far superior when compared to the mixed (NHC)(phosphine) catalysts known thus far.     

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) nanocomposites with multiple properties in the DMF‐toluene mixture solvent

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) (Ag/(PDMS‐b‐PMMA)) hybrid nanocomposites was proposed by using the siloxane‐containing block copolymers as stabilizer. The reduction of silver nitrate (AgNO₃) was performed in the mixture solvent of dimethyl formamide (DMF) and toluene, which was used to dissolve double‐hydrophobic copolymer, as well as served as the powerful reductant. The presence of the PMMA block in the copolymer indeed exerted as capping ligands for nanoparticles. The resultant nanocomposites exhibited super hydrophobicity with water contact angle of 123.3^° and the thermogravimetry analysis (TGA) revealed that the resultant nanocomposites with more PDMS were more heat‐resisting. Besides, the antimicrobial efficiency of the most desirable nanocomposite (Ag/PDMS₆₅‐b‐PMMA₃₀ loaded with 7.3% silver nanoparticle) could reach up to 99.4% when contacting with escherichia coli within 120 min. As a whole, the resultant nanocomposites by the integration of excellent properties of silver nanoparticles as well as siloxane‐block copolymers can be a promising for the development of materials with hydrophobic, heat‐resisting and outstanding antibacterial properties from the chemical product engineering viewpoint. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4780–4793, 2013     

Adducts of silver(I) nitrite with triphenylphosphine and N,N′-bidentate aromatic bases,L, of the form AgNO2:PPh3:L (1:1:1)

Adducts of the form AgNO₂:PPh₃: L (1:1:1) (L = 2,2′-bipyridyl (bpy), 1,10-phenanthroline (phen), 2,9-dimethylphenanthroline (dmp)) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H and ³¹P NMR) studies, together with a single crystal X-ray study for the L = dmp adduct, for comparison with the recently reported counterpart adducts of silver(I) nitrate. While the silver(I) coordination environment is still dominated by the quasi-planar N₂AgP motif (Ag–P 2.378(1), Ag–N 2.364(3), 2.392(4) Å), the interaction of the nitrite is symmetrical (Ag–O 2.512(4), 2.543(5) Å) and invasive, the PAgN₂ angle sum diminished to 324.7°.     

Silver–polyimide nanocomposite membranes: Macromolecular‐matrix‐mediated metallization of an aromatic,fluorinated polyimide yielding highly reflective films at low metal concentrations

Highly reflective, surface‐metalized, flexible polyimide films were prepared by the incorporation of a soluble silver‐ion complex, (hexafluoroacetylacetonato)silver(I) (AgHFA), into dimethylacetamide solutions of poly(amic acid) prepared from 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane. The thermal curing of solution‐cast silver(I)–poly(amic acid) films to 300°C led to cycloimidization of the amic acid with concomitant silver(I) reduction and the formation of a reflective, air‐side‐silvered surface at very low (2 wt % and 0.3 vol %) silver concentrations. The reflective surface evolved only when the cure temperature reached about 275°C, although X‐ray diffraction showed metallic silver in the hybrid film by 200°C. After a maximum specular reflectivity greater than 80% was achieved for the 2 wt % silver film, the specular reflectivity diminished sharply with further heating at a constant temperature of 300°C. Incorporating the AgHFA complex into the soluble, fully imidized form of poly{(1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐2,5‐diyl)[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene](1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐5,2‐diyl)‐1,4‐phenyleneoxy‐1,4‐phenylene[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene]‐1,4‐phenyleneoxy‐1,4‐phenylene} gave films that were 25% less reflective than those beginning with poly(amic acid). Though highly reflective, the films were not electrically conductive. The metalized membranes were thermally stable and maintained mechanical properties similar to those of the parent polyimide. Transmission electron microscopy revealed an air‐side, near‐surface layer of silver that was about 40 nm thick; the interior of the film had well‐dispersed metal particles with diameters mostly less than 2 nm. The near‐surface silver layer maintained its integrity because of physical entrapment of the metal nanoparticles beneath a thin layer of polyimide; that is, the practical adhesion of the metal layer was good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2409–2418, 2007