Production of H2 and Glucaric Acid Using Electrocatalyst Glucose Oxidation by the Ta NiFe LDH Electrode.

The slow anodic oxygen evolution reaction (OER) significantly limits electrocatalytic water splitting for hydrogen production. We proposed the electrocatalyst for glucose oxidation by Ta-doping NiFe LDH nanosheets to simultaneously obtain glucaric acid (GRA) and hydrogen gas as a useful byproduct. Superior glucose oxidation reaction (GOR) activity is demonstrated by the optimized Ta-NiFe LDH, which has a low overpotential of 192 mV, allowing for a small Tafel slope of 70 mV dec-1 and a current density of 50 mA cm-2. The Ta NiFe LDH-oxidized glucose to GRA with a 72.94% yield and 64.3% Faradaic efficiency at 1.45 VRHE. Herein, we report the Ta NiFe LDH/NF electrode for the GOR&hydrogen evolution reaction (HER), which exhibits a cell voltage of 1.62 V to reach a current density of 10 mA cm-2, which is 250 mV lower compared to OER&HER (1.87 V). This study reveals that GOR is an energy-efficient and cost-effective method for producing H2 and valorizing biomass.

Electrocatalytic Reactions for Converting CO2 to Value-Added Products: Recent Progress and Emerging Trends.

Carbon dioxide (CO2) emissions are an important environmental issue that causes greenhouse and climate change effects on the earth. Nowadays, CO2 has various conversion methods to be a potential carbon resource, such as photocatalytic, electrocatalytic, and photo-electrocatalytic. CO2 conversion into value-added products has many advantages, including facile control of the reaction rate by adjusting the applied voltage and minimal environmental pollution. The development of efficient electrocatalysts and improving their viability with appropriate reactor designs is essential for the commercialization of this environmentally friendly method. In addition, microbial electrosynthesis which utilizes an electroactive bio-film electrode as a catalyst can be considered as another option to reduce CO2. This review highlights the methods which can contribute to the increase in efficiency of carbon dioxide reduction (CO2R) processes through electrode structure with the introduction of various electrolytes such as ionic liquid, sulfate, and bicarbonate electrolytes, with the control of pH and with the control of the operating pressure and temperature of the electrolyzer. It also presents the research status, a fundamental understanding of carbon dioxide reduction reaction (CO2RR) mechanisms, the development of electrochemical CO2R technologies, and challenges and opportunities for future research.

Photoelectrochemical Epoxidation of Cyclohexene on an α-Fe2O3 Photoanode Using Water as the Oxygen Source.

This study developed a safe and sustainable route for the epoxidation of cyclohexene using water as the source of oxygen at room temperature and ambient pressure. Here, we optimized the cyclohexene concentration, volume of solvent/water (CH3CN, H2O), time, and potential on the photoelectrochemical (PEC) cyclohexene oxidation reaction of the α-Fe2O3 photoanode. The α-Fe2O3 photoanode epoxidized cyclohexene to cyclohexene oxide with a 72.4 ± 3.6% yield and a 35.2 ± 1.6% Faradaic efficiency of 0.37 V vs Fc/Fc+ (0.8 VAg/AgCl) under 100 mW cm-2. Furthermore, the irradiation of light (PEC) decreased the applied voltage of the electrochemical cell oxidation process by 0.47 V. This work supplies an energy-saving and environment-benign approach for producing value-added chemicals coupled with solar fuel generation. Epoxidation with green solvents via PEC methods has a high potential for different oxidation reactions of value-added and fine chemicals.

Development of Low-Shrink Epoxy Putty to Solve Appearance-Quality Defects of Carbon-Fiber-Reinforced Plastic Automotive Exterior Parts.

In this study, epoxy putties with novel compositions were developed for the filling of structural voids in carbon-fiber-reinforced plastics (CFRPs), which are used to fabricate automotive parts. Two constituent solutions-one consisting of epoxy resins and the other consisting of a hardener-were formulated, mixed, and then coated on CFRP surfaces, followed by curing. The surfaces were then evaluated to determine the shrinkage rates (calculated based on the liquid densities and cured mixtures), adhesion properties (determined by a peel test), and color differences (measured with a colorimeter) of the synthesized putties. The last two properties were compared with those of the commercially available putties to ascertain the thermal resistance of the developed putties. The results indicated that the synthesized epoxy putties were more strongly adhesive and exhibited less difference in color. Furthermore, after thermal impact, both the adhesive properties and color stabilities of the synthesized epoxy putties were found to be superior to those of the commercial putty.

Synthesis of Waterborne Polyurethane Using Phosphorus-Modified Rigid Polyol and its Physical Properties.

In this study, a phosphorous-containing polyol (P-polyol) was synthesized and reacted with isophorone diisocyanate (IPDI) to produce water-dispersed polyurethane. To synthesize waterborne polyurethanes (WPUs), mixtures of P-polyol and polycarbonate diol (PCD) were reacted with IPDI, followed by the addition of dimethylol propionic acid, to confer hydrophilicity to the produced polyurethane. An excess amount of water was used to disperse polyurethane in water, and the terminal isocyanate groups of the resulting WPUs were capped with ethylene diamine. P-polyol:PCD molar ratios of 0.1:0.9, 0.2:0.8, and 0.3:0.7 were used to synthesize WPUs. The films prepared by casting and drying the synthesized WPUs in plastic Petri dishes were used to test the changes in physical properties induced by changing the P-polyol:PCD molar ratio. The experimental results revealed that the tensile strength of PU-10, the WPU with a P-polyol:PCD molar ratio of 0.1:0.9, was 16% higher than that of the reference P-polyol-free WPU sample. Moreover, the thermal decomposition temperature of PU-10 was 27 °C higher than that of the reference sample.

Flame Retardant Submicron Particles via Surfactant-Free RAFT Emulsion Polymerization of Styrene Derivatives Containing Phosphorous.

The reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of diethyl-(4-vinylbenzyl) phosphate (DEVBP) was performed using PEG-TTC as a macro RAFT agent. PEG-TTC (MW 2000, 4000) was synthesized by the esterification of poly (ethylene glycol) methyl ether with a carboxylic-terminated RAFT agent, composed a hydrophilic poly (ethylene glycol) (PEG) block and a hydrophobic dodecyl chain. The RAFT emulsion polymerization of DEVBP was well-controlled with a narrow molecular size distribution. Dynamic light scattering and confocal laser scanning microscopy were used to examine the PEG-b-PDVBP submicron particles, and the length of the PEG chain (hydrophilic block) was found to affect the particle size distribution and molecular weight distribution. The submicron particle size increased with increasing degree of polymerization (35, 65, and 130), and precipitation was observed at a high degree of polymerization (DP) using low molecular weight PEG-TTC (DP 130, A3). The flame retardant properties of the PEG-b-PDVBP were evaluated by thermogravimetric analysis (TGA) and micro cone calorimeter (MCC). In the combustion process, the residue of PEG-b-PDEVBP were above 500 °C was observed (A1 ~ B3, 27 ~ 38%), and flame retardant effect of PEG-b-PDEVBP submicron particles/PVA composite were confirmed by increasing range of temperature and decreasing total heat release with increasing contents of PEG-b-PDEVBP. The PEG-b-PDEVBP submicron particles can provide flame retardant properties to aqueous, dispersion and emulsion formed organic/polymer products.

Highly Flexible Graphene Derivative Hybrid Film: An Outstanding Nonflammable Thermally Conductive yet Electrically Insulating Material for Efficient Thermal Management.

In modern society, advanced technology has facilitated the emergence of multifunctional appliances, particularly, portable electronic devices, which have been growing rapidly. Therefore, flexible thermally conductive materials with the combination of properties like outstanding thermal conductivity, excellent electrical insulation, mechanical flexibility, and strong flame retardancy, which could be used to efficiently dissipate heat generated from electronic components, are the demand of the day. In this study, graphite fluoride, a derivative of graphene, was exfoliated into graphene fluoride sheets (GFS) via the ball-milling process. Then, a suspension of graphene oxide (GO) and GFSs was vacuum-filtrated to obtain a mixed mass, and subsequently, the mixed mass was subjected to reduction under the action hydrogen iodide at low temperature to transform the GO to reduced graphene oxide (rGO). Finally, a highly flexible and thermally conductive 30-µm thick GFS@rGO hybrid film was prepared, which showed an exceptional in-plane thermal conductivity (212 W·m-1·K-1) and an excellent electrical insulating property (a volume resistivity of 1.1 × 1011 Ω·cm). The extraordinary in-plane thermal conductivity of the GFS@rGO hybrid films was attributed to the high intrinsic thermal conductivity of the filler components and the highly ordered filler alignment. Additionally, the GFS@rGO films showed a tolerance to bending cycles and high-temperature flame. The tensile strength and Young's modulus of the GFS@rGO films increased with increasing the rGO content and reached a tensile strength of 69.3 MPa and a Young's modulus of 10.2 GPa at 20 wt % rGO. An experiment of exposing the films to high-temperature flame demonstrated that the GFS@rGO films could efficiently prevent fire spreading. The microcombustion calorimetry results indicated that the GFS@rGO had significantly lower heat release rate (HRR) compared to the GO film. The peak HRR of GFS@rGO10 was only 21 W·g-1 at 323 °C, while that of GO was 198 W·g-1 at 159 °C.

Modified Epoxy Resin Synthesis from Phosphorus-Containing Polyol and Physical Changes Studies in the Synthesized Products.

Epoxy resins are commonly used to manufacture the molding compounds, reinforced plastics, coatings, or adhesives required in various industries. However, the demand for new epoxy resins has increased to satisfy diverse industrial requirements such as enhanced mechanical properties, thermal stability, or electrical properties. Therefore, in this study, we synthesized new epoxy resin (PPME) by modifying phosphorous-containing polyol. The prepared resin was analyzed and added to epoxy compositions in various quantities. The compositions were cured at high temperatures to obtain plastics to further test the mechanical and thermal properties of the epoxy resin. The measured tensile and flexural strength of epoxy compositions were similar to the composition without synthesized epoxy resin. However, the heat release rates of the compositions exhibited tendencies of a decrease proportional to the amount of PPME.

Clarifying the mechanism of cation exchange in Ca(II)[15-MC(Cu(II)ligand)-5] complexes.

The calcium metallacrown Ca(II)[15-MC(Cu(II)N(Trpha))-5](2+) was obtained by self-assembly of Ca(II), Cu(II), and tryptophanhydroxamic acid. Its X-ray structure shows that the core calcium ion is well-encapsulated in the five oxygen cavity of the metallacrown scaffold. The kinetics of Ca-Ln core metal substitution was studied by visible spectrophotometry by addition of Ln(III) nitrate to solutions of Ca(II)[15-MC(Cu(II)N(Trpha))-5](2+) in methanol solution at pH 6.2 (Ln(III) = La(III), Nd(III), Gd(III), Dy(III), Er(III)) to obtain the corresponding Ln(III)[15-MC(Cu(II)N(Trpha))-5](3+) complexes on the hours time scale. The reaction is first order in the two reactants (second order overall) with different rate constants across the lanthanide series. In particular, the rate for the Ca-Ln substitution decreases from La(III) to Gd(III) and then increases slightly from Gd(III) to Er(III). This substitution reaction occurs with second order rate constants ranging from 0.1543(3) M(-1) min(-1) for La(III) to 0.0720(6) M(-1) min(-1) for Gd(III). By means of the thermodynamic log K constants for the same reaction previously reported, the rate constants for the inverse Ln-Ca substitution were also determined. In this study, we demonstrated that the substitution reaction proceeds through a direct metal substitution and does not involve the disassembly of the MC scaffold. These observations in concert allow the proposition of a hypothesis that the dimension of the core metals play the major role in determining the rate constants of the substitution reaction. In particular, the largest lanthanides, which do not require complete encapsulation in the MC cavity, displace the Ca(II) ion faster, whereas in the back reaction Ca(II) displaces the smaller lanthanides faster as they interact relatively weakly with the metallacrown oxygen cavity.

A chemical precursor for depositing Sb2S3 onto mesoporous TiO2 layers in nonaqueous media and its application to solar cells.

Deposition of nanocrystalline Sb(2)S(3) onto a mesoporous TiO(2) photoanode is an important process in the fabrication of Sb(2)S(3)-sensitized solar cells. In order to generate oxide-free nanosized Sb(2)S(3), a single-source precursor for the chemical bath deposition of Sb(2)S(3) in nonaqueous media, Sb(III)(thioacetamide)(2)Cl(3), was synthesized and used to produce high-quality Sb(2)S(3) for solar cells.

Panchromatic photon-harvesting by hole-conducting materials in inorganic-organic heterojunction sensitized-solar cell through the formation of nanostructured electron channels.

Additional photon-harvesting by hole transporting materials in Sb(2)S(3)-sensitized solar cell is demonstrated through the formation of electron channels in the hole transporter such as P3HT (poly(3-hexylthiophene)) and PCPDTBT(poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) that can act as both a hole conductor and light absorber. As a result, the short-circuit current density is improved with an increment in overall efficiency. These findings provide new insights into use of light-absorbing conjugated polymers as a hole conductor in the inorganic-organic heterojunction sensitized solar cells.

Influencing the size and anion selectivity of dimeric Ln(3+)[15-metallacrown-5] compartments through systematic variation of the host side chains and central metal.

Dimeric Ln(3+)[15-metallacrown-5] compartments selectively recognize carboxylates through guest binding to host metal ions and intermolecular interactions with the phenyl side chains. A systematic study is presented on how the size, selectivity, and number of encapsulated guests in the dimeric containers is influenced by the Ln(3+)[15-metallacrown(Cu(II))-5] ligand side chain and central metal. Compartments of varying heights were assembled from metallacrowns with S-phenylglycine hydroxamic acid (pgHA), S-phenylalanine hydroxamic acid (pheHA), and S-homophenylalanine hydroxamic acid (hpheHA) ligands. Guests that were examined include the fully deprotonated forms of terephthalic acid, isonicotinic acid, and bithiophene dicarboxylic acid (btDC). X-ray crystallography reveals that the side-chain length constrains the maximum and minimum length guest that can be encapsulated in the compartment. Compartments with heights ranging from 9.7 to 15.2 Å are formed with different phenyl side chains that complex 4.3-9.2 Å long guests. Up to five guests are accommodated in Ln(3+)[15-metallacrown(Cu(II))-5] compartments depending on steric effects from the host side chains. The nine-coordinate La(3+) central metal promotes the encapsulation of multiple guests, while the eight-coordinate Gd(3+) typically binds only one dicarboxylate. Electrospray ionization mass spectrometry reveals that the dimerization phenomenon occurs beyond the solid state, suggesting that these containers can be utilized in solid-state and solution applications.

Enhancing the device performance of Sb2S3-sensitized heterojunction solar cells by embedding Au nanoparticles in the hole-conducting polymer layer.

Performance of Sb(2)S(3)-sensitized heterojunction solar cells is enhanced by embedding Au nanoparticles in the poly-3-hexylthiophene (P3HT) hole-conducting polymer layer. The improved charge transfer/transport at the Sb(2)S(3)/P3HT/Au interface by extended interface area of the P3HT/Au counter electrode and the re-absorption of the backscattering light from the embedded Au nanoparticles enhanced the device performance: J(sc) 11.0 to 12.8 mA cm(-2), V(oc) 606 to 626 mV, fill factor (FF) 60.5 to 61.2%, and power conversion efficiency (η) 4.0 to 4.9%. Simultaneous enhancement of V(oc), J(sc), and FF in Au nanoparticle-embedded systems is mainly attributed to the improved charge collection efficiency and light harvesting efficiency of Sb(2)S(3) due to the improved charge transfer/transport in the Sb(2)S(3)/P3HT/Au interface.

Improvement of external quantum efficiency depressed by visible light-absorbing hole transport material in solid-state semiconductor-sensitized heterojunction solar cells.

A mesoporous (mp)-TiO(2)/Sb(2)S(3)/P3HT [poly(3-hexylthiophene)] heterojunction solar cell displays reduced external quantum efficiency (EQE) at a wavelength of approximately 650 nm. This loss in EQE is due to incomplete charge carrier transport because the transportation of charge carriers generated in P3HT by the absorption of light into Sb(2)S(3) was inefficient, and consequently, the carriers recombined. The depression of the EQE was greatly relieved by introducing the porous structure formed by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN) into the P3HT layer.

Toward interaction of sensitizer and functional moieties in hole-transporting materials for efficient semiconductor-sensitized solar cells.

Sb(2)S(3)-sensitized mesoporous-TiO(2) solar cells using several conjugated polymers as hole-transporting materials (HTMs) are fabricated. We found that the cell performance was strongly correlated with the chemical interaction at the interface of Sb(2)S(3) as sensitizer and the HTMs through the thiophene moieties, which led to a higher fill factor (FF), open-circuit voltage (V(oc)), and short-circuit current density (J(sc)). With the application of PCPDTBT (poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)) as a HTM in a Sb(2)S(3)-sensitized solar cell, overall power conversion efficiencies of 6.18, 6.57, and 6.53% at 100, 50, and 10% solar irradiation, respectively, were achieved with a metal mask.

Effects of the central lanthanide ion crystal radius on the 15-MC(Cu(II)(N)pheHA)-5 structure.

Twenty crystal structures of the Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complex, where pheHA = phenylalanine hydroxamic acid and where Ln(III) = Y(III) and La(III)-Tm(III), except Pm(III), with the nitrate and/or hydroxide anion are used to assess the effect of the central metal ion on the metallacrown structure. Each Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complex is amphiphilic with a hydrophobic side consisting of the phenyl groups of the pheHA ligand and a side without the aromatic residues. Three general structures are observed for the Ln(III)[15-MC(CuII(N)pheHA)-5](3+) complexes. In the Type 1 structures, the central metal ion does not bind a nitrate anion on the metallacrown's hydrophobic face, and two adjacent metallacrowns dimerize through their phenyl groups producing a hydrophobic compartment. In the Type 2 structures, the central metal ion binds a nitrate in a bidentate fashion on the hydrophobic face. There are two distinct types of Type 2 metallacrowns, designated A and B. Type 2A metallacrowns have a water molecule bound to the central metal ion on the hydrophilic face, while Type 2B metallacrowns have a monodentate nitrate ion bound on the hydrophilic face to the central metal ion. The Type 2 metallacrowns also dimerize via the phenyl groups to form a hydrophobic compartment. In Type 3 structures, the central metal ion binds a nitrate in a bidentate fashion on the hydrophobic side, but instead of forming dimers, the metallacrowns pack in a helical arrangement to give either P or M one-dimensional helices. Regardless of the type of metallacrown, the overall trend observed is that as the Ln(III) ion crystal radius increases, the metallacrown cavity radius also increases while the metallacrown becomes more planar. This conclusion is demonstrated by a decrease in the oxime oxygen distances to the oxime oxygen mean plane and a decrease in the ring Cu(II) distances to the Cu(II) mean plane as the metallacrown cavity radius increases and the lanthanide crystal radius increases. In addition, a decrease in the O(oxime)-Cu(II)-N(oxime)-O(oxime) torsion (dihedral) angles is also observed as the metallacrown cavity radius and the lanthanide crystal radius both increase. These observations help explain the thermodynamic preferences for Ln(III) ions within this class of metallacrowns and may be used to design compartments capable of binding guests in different orientations within chiral, soft solids.

Gd(III)[15-metallacrown-5] recognition of chiral α-amino acid analogues.

Chiral Ln(III)[15-metallacrown-5] complexes with phenyl side chains have been shown to encapsulate aromatic carboxylates reversibly in their hydrophobic cavities. Given the importance of selective guest binding for applications of supramolecular containers in synthesis, separations, and materials design, the affinity of Gd(III)[15-metallacrown(Cu(II), L-pheHA)-5] hosts for a series of chiral carboxylate guests with varying substitutions on the α-carbon (phenylalanine, N-acetyl-phenylalanine, phenyllactate, mandelate, methoxyphenylacetate) has been investigated. Differential binding of S- and R-phenylalanine was revealed by X-ray crystallography, as the S-enantiomer exclusively forms associative hydrogen bonds with oxygen atoms in the metallacrown ring. Selective guest binding in solution was assessed with isothermal titration calorimetry, which measures the sequential guest binding in the hydrophobic cavity first and the hydrophilic face of the host, and a cyclic voltammetry assay, which quantifies guest binding strength in the hydrophobic cavity of the host exclusively. In solution, the Gd(III)[15-metallacrown(Cu(II), L-pheHA)-5] hydrophobic cavity exhibits modest chiral selectivity for enantiomers of phenylalanine (K(S)/K(R) = 2.4) and mandelate (K(S)/K(R) = 1.22). Weak binding constants of ∼100 M(-1) were measured for neutral and -1 charged carboxylates with hydrophilic functional groups (ammonium, N-acetyl, methyl ether). Weaker binding relative to the unsubstituted guests is attributed to unfavorable interactions between the hydrophilic functionalities of the guest and the hydrophobic cavity of the host. In contrast, binding constants greater than 2000 M(-1) were measured for α-hydroxy analogues phenyllactate and mandelate. The significantly increased affinity likely arises from the guests being bound as a -2 anion upon metal-assisted deprotonation in the Gd(III)[15-metallacrown(Cu(II), l-pheHA)-5] cavity. It is established that guest binding affinity in the hydrophobic cavity of the host follows the general trend of neutral zwitterion < monoanion < dianion, with hydrophilic functional groups decreasing the binding affinity. These results have broad implications for the development of metallacrowns as supramolecular catalysts or in chiral separations.

Metal-dependent phase selection in coordination polymers derived from a C(2V)-symmetric tricarboxylate.

Reacting biphenyl-3,4',5-tricarboxylic acid (H(3)BHTC) with the appropriate metal salt yields the microporous coordination polymers (MCPs) Mn(3)(BHTC)(2) (1), Mg(3)(BHTC)(2) (2), and Co(3)(BHTC)(2) (3) containing hourglass metal clusters. The addition of Cu to reactions with Co(II), Fe(III), or Mn(II) leads to the formation of heterobimetallic UMCM-150 isostructural analogues Co(1)Cu(2)(BHTC)(2) (4), Fe(1)Cu(2)(BHTC)(2) (5), and Mn(1)Cu(2)(BHTC)(2) (6) containing both paddlewheel and trinuclear metal clusters. X-ray diffraction analysis of the crystals of the heterobimetallic MCPs suggests that Cu on the trinuclear site of UMCM-150 was replaced by the other metal, whereas Cu in paddlewheel sites remains unchanged. N(2) sorption isotherms were measured for the mixed-metal UMCM-150 analogues, and it was confirmed that there is no structural collapse after the metal replacement.

Thermodynamics of core metal replacement and self-assembly of Ca(2+) 15-metallacrown-5.

The equilibria for core Ca(2+) replacement by Ln(3+) in copper(II) 15-MC-5 complexes have been investigated using a series of visible spectrophotometric titrations of calcium(II) metallacrowns ({Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+)) with Ln(3+) ions (H(2)L = pheha, (S)-alpha-phenylalaninehydroxamic acid, or trpha, (S)-alpha-tryptophanhydroxamic acid). These studies allowed the determination of the equilibrium constants for the reaction {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) + Ln(3+) --> {Ln(III)[15-MC(Cu(II)(N)(L))-5]}(3+) + Ca(2+) in methanol/water 9:1 (Ln(3+) = La(3+), Gd(3+), Dy(3+), Er(3+)) or 99:1 (Ln(3+) = La(3+), Nd(3+), Gd(3+), Dy(3+), Er(3+), Yb(3+)), respectively. The log K for these reactions decreases with increasing atomic number of the lanthanide(III), ranging from 6.1 to 3.91 in methanol/water 9:1. The same behavior is observed in methanol/water 99:1, although the constants are uniformly lower (log K = 4.09-2.52). A significant thermodynamic selectivity was observed for the later lanthanides (Gd(3+)-Yb(3+)) while a smaller selectivity is present throughout the beginning of the series (La(3+)-Gd(3+)). This observation has been interpreted on the basis of the size correspondence between the metal ions and the metallacrown cavity. The overall stability of the {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) in methanol/water 9:1 has been determined by pH-spectrophotometric titrations with HCl. The resulting log K values are 63.46(12) and 65.05(13) for pheha and trpha, respectively (Ca(2+) + 5Cu(2+) + 5HL(-) = {Ca(II)[15-MC(Cu(II)(N)(L))-5]}(2+) +5H(+)). The stability of both the La(3+) and Ca(2+) 15-metallacrown-5 complexes in the presence of high Na(+) concentrations has also been demonstrated by spectophotometric studies. Based upon these observations, the preference of the 15-MC-5 for Ca(2+) complexation compared to crown ethers has been quantitatively demonstrated for the first time.