Two phenol-based compartmental ligands of the “end-off” type, 2,6-bis{N-[2-(dimethylamino)ethyl]iminomethyl}-4-methylphenol (HL1) and 2-{N-[2-(dimethylamino)ethyl]iminomethyl}-6-{N-methyl-N-[2-(dimethylamino)ethyl]aminomethyl}-4-bromophenol (HL2), have been used to form [Ni2(L1)(AcO)(NCS)2(MeOH)] (1), [Ni2(L1)(AcO)2(MeOH)]BPh4 (2), [Ni2(L2)(AcO)(NCS)2(MeOH)] (3), [Ni2(L2)(AcO)2]BPh4 (4), and [Ni2(L2)(NCS)3(MeOH)] (5). X-ray crystallographic studies were done for 2−5. 2:  triclinic, space group P1̄, a = 13.613(3) Å, b = 16.475(4) Å, c = 11.307(4) Å, α = 99.90(2)°, β = 104.16(2)°, γ = 109.01(2)°, V = 2253(1) Å3, Z = 2. The complex cation has a dinuclear core triply bridged by the phenolic oxygen of (L1)- and two acetate groups in the syn-syn mode. One Ni has a six-coordinate geometry together with a methanol oxygen. 3: triclinic, space group P1̄, a = 10.167(1) Å, b = 16.119(2) Å, c = 9.472(3) Å, α = 103.53(2)°, β=100.91(1)°, γ = 85.62(1)°, V = 1481(1) Å3, Z = 2. A pair of Ni ions are bridged by the phenolic oxygen of (L2)-, an isothiocyanate nitrogen, and an acetate group. The sixth position of one Ni is occupied by a methanol oxygen and that of the other Ni by isothiocyanate nitrogen. 4:  monoclinic, space group P21/n, a = 15.146(2) Å, b = 9.442(3) Å, c = 30.844(2) Å, β = 93.427(9)°, V = 4402(1) Å3, Z = 4. Two Ni ions are bridged by the phenolic oxygen of (L2)- and an acetate group. The Ni bound to the iminic pendant arm is nearly planar whereas the Ni bound to the aminic pendant arm is of six-coordination together with a bidentate acetate group. 5:  monoclinic, space group C2/c, a = 26.744(5), b = 10.323(4) Å, c = 21.785(6) Å, β = 94.73(2)°, V = 5993(3) Å3, Z = 8. Two Ni ions are bridged by the phenolic oxygen of (L2)- and an isothiocyanate nitrogen. The Ni bound to the iminic pendant arm is of five-coordination along with an isothiocyanate nitrogen. The Ni bound to the aminic pendant arm has a six-coordinate geometry together with a methanol oxygen and an isothiocyanate nitrogen. 1−5 were examined regarding their ability to bind urea, and 4 and 5 were shown to form [Ni2(L2)(AcO)2(urea)]BPh4 (4‘) and [Ni2(L2)(NCS)3(urea)] (5‘), respectively. 5‘ crystallizes in the monoclinic system, space group P21/n, with a = 11.709(5), b = 15.100(4), c = 17.548(5) Å, β = 95.58(3)°, V = 3087(1) Å3, and Z = 4. Its dinuclear core is very similar to that of 5 except that the methanol of 5 is replaced by a urea molecule.

1,3-Bis[(2-dimethylaminoethyl)iminomethyl]benzene (baib), having two isolated metal-binding sites separated by a m-xylenylene group, formed dinuclear metal() complexes [Mn 2 (baib)(O 2 CPh) 3 ]BPh 4 ؒMeCN 1, [Mn 2 (baib)-(O 2 CPh) 3 (NCS)] 2, [Co 2 (baib)(O 2 CMe) 3 ]BPh 4 3, [Co 2 (baib)(O 2 CPh) 3 ]BPh 4 4 and [Zn 2 (baib)(O 2 CMe) 3 ]BPh 4 5. The structure of a dimethylformamide adduct of 2, [Mn 2 (baib)(O 2 CPh) 3 (NCS)]ؒdmf 2Ј, was determined. It has a dinuclear core bridged by two benzoate groups in the symmetric η 1 :η 1 mode and one benzoate group in the asymmetric η 1 :η 2 mode, with a Mn ؒ ؒ ؒ Mn separation of 3.501(4) Å. A thiocyanate ion co-ordinates to one Mn through its nitrogen; both manganese ions are six-co-ordinated. Complex 3 was also characterized crystallographically. The pair of cobalt ions are bridged by three acetate groups in the η 1 :η 1 mode with a Co ؒ ؒ ؒ Co intermetallic separation of 3.449(2) Å. The geometry about each Co is a trigonal bipyramid. The complexes 4ؒMeCN (4Ј) and 5 have dinuclear cores essentially similar to that of 3: Co ؒ ؒ ؒ Co 3.482(2) and Zn ؒ ؒ ؒ Zn 3.4648(7) Å. The physicochemical properties of the complexes are reported together with the catalase-like function of 1-3.

We have invented a new device based on atomic force microscopy that measures the emission from a single microparticle by force direct application using the AFM probe, and successfully observed emission in the region of the elastic deformation, friction, and destructive deformation.

Analysis of Cu(I) in copper sulfate electroplating solution was conducted by absorption of a chelate of Cu(I) with bathocuproinedisulfonic acid, disodium salt (BCS). Although the absorption of new copper sulfate electroplating solutions was negligible, the absorption of operating solutions was clear. The difference of new solutions and operating solutions was also verified using an electrochemical method for detection of Cu(I). We concluded that the Cu(I) ions are measurable using this chelate reagent. The absorption increased quickly in a few minutes after mixing with the chelate reagent and subsequently continued to increase slowly. To clarify this phenomenon, the organic compounds in the plating solutions were analyzed and Cu(I)-PEG (polyethylene glycol) complexes with different chain lengths were detected using MALDI-MS. Results show that Cu(I) ions exist in the plating solutions not only as small complexes with small organic compounds but also as large complexes with PEG. Small complexes of Cu(I) can react quickly with BCS and cause the rapid increase of the absorption in a few minutes after mixing. Cu(I)-PEG complexes prevent the chelating reaction of Cu(I) with BCS by steric hindrance of PEG, which explains the subsequent slow increase of the absorption. Using this chelate method, we monitored quantities of Cu(I) in copper sulfate electroplating production lines, detected the variation of Cu(I) quantities, and found the increase during the resting state of the lines.

Analysis of Cu(I) in copper sulfate electroplating solutions was conducted by absorption of a chelate of Cu(I) with bathocuproinedisulfonic acid, disodium salt (BCS). The absorbance of the color reaction of Cu(I) increased quickly in a few minutes after mixing with the chelate reagent and subsequently continued to increase slowly. To analyze the reaction kinetics of the color reaction, we divided Cu(I) complexes into two groups, small complexes and large Cu(I)-PEG complexes, and assumed the reaction of each group of complexes and BCS is a first order reaction with a specific reaction rate constant. We simulated the absorption curve with a good correlation and obtained the concentrations and the time constants, inverse of rate constants, of small complexes and large Cu(I)-PEG complexes. These concentrations and time constants are important parameters to control plating solutions. The time constant of small complexes can be attributed to the variation of the proportions of these small complexes. The smaller time constant of Cu(I)-PEG complexes can be considered the larger size distribution of Cu(I)-PEG with different chain lengths. Using this analysis, we monitored the variation of Cu(I) concentration in production lines for one month and found the increase of small complexes during the resting state of the lines. This increase corresponded to the tendency of occurring of brightening troubles.