Jan K. Herrema

SYNTHESIS AND REACTIVITY OF TRIGONAL COPPER(I) COMPOUNDS. CRYSTAL STRUCTURE OF BIS(TETRAHYDROPYRIMIDINE-2-THIONE)COPPER(I) BROMIDE

Reaction of monovalent copper halides with excess tetrahydropyrimidine-2-thione (thpmtH(2)) in acetonitrile results in the formation of three-coordinate monomer products of formula Cu(thpmtH(2))(2)X. The crystal and molecular structure of the bromo complex is reported and discussed with respect to analogous copper(I) complexes. The compound crystallizes in the tetragonal system, space group, P4(1)2(1)2 with a = 8.005(1), c = 21.3 1(1) Angstrom, and Z = 4. The two Cu-S bonds are 2.215(4) A and the Cu-Br bond distance is 2.405(2) Angstrom, the interbond angles around copper being exactly 360 degrees. Reactivity of the title compound as well as of its iodo counterpart towards Lewis bases was also investigated; the two compounds react readily, in stoicheiometric amounts, with tertiary phosphine and arsine ligands forming monomeric four-coordinate Cu(I) species, the structures of which were deduced by spectroscopic measurements.

Synthesis of poly[(silanylene)thiophene]s

Poly[(silanylene)thiopene]s, copolymers with alternating thiophene, 2,2′-bithiophene, or 2,2′:5′,5″-terthiophene and mono-, di-, or tetrasilanylene units, were prepared by condensation of the dilithium salts of the thiophenes or the bis(2′-thienyl)silanes with α,ω-dichlorosilanes in diethylether. The polymers were characterized with1H,13C, and29Si NMR, UV, IR, GPC, TGA, and elemental analyses. UV absorption maxima of these polymers all show a red shift with increasing length of the polymer backbone, suggesting that conjugation occurs through the combined σ-Si and π-thiophene backbone.

Methyl Valerenate, a New Sesquiterpenoid in the Essential Oil from Underground Parts of Valeriana officinalis L. s.l.

Abstract A new valerenane sesquiterpenoid, methyl valerenate (1), was found in the essential oil from underground parts of Valeriana officinalis L. s.l. Spectral data of methyl valerenate, which was synthesized from valerenic acid (2), are given in this paper.

Structural and spectroscopic characterization of copper(I) halogen complexes with omega-thiocaprolactam and triphenylphosphine

A series of mixed ligand copper(I) halogeno complexes with omega-thiocaprolactam, (tclH) and triphenylphosphine (PPh(3)) of general formula Cu(tclH)(n)(PPh(3))(3-n)X where n = 1, 2 and X = CI, Pr, I has been studied. The crystal structure of Cu(tclH)(PPH3)(2)Br is reported and discussed with respect to those of other members of the series. Solution C-13 and P-31 NMR spectra of the compounds are related to structural characteristics. Cu(tclH)(PPH3)(2)Br crystallizes in the monoclinic system, space group P2(1)/c, with a = 16.11(2), b = 9.749(2), c = 26.46(3)Angstrom, beta = 91.03(5)degrees and Z = 4. The local copper environment is irregular tetrahedral with Cu-P equal to 2.289(4) and 2.277(4)Angstrom, while Cu-S and Cu-Br are 2.344(4) and 2.522(2)Angstrom, respectively.

COLOR TUNING OF POLY[(SILANYLENE)THIOPHENE] BLOCK-COPOLYMERS

Block copolymers are materials where control over luminescence can be achieved by means of adjusting the length of the active ((pi) conjugated) block. We report on electroluminescent devices from poly[(Silanylene)Thiophene] block copolymers.