Variationen modulo 4–4+, 4+3–3+4–, 4–5+, 5–4+4–5+4–4+ bei Seltenerdcarbidhalogeniden

The new compounds Pr₈(C₂)₄Cl₅ (1), Pr₁₄(C₂)₇Cl₉ (2), Pr₂₂(C₂)₁₁Cl₁₄ (3), Ce₂(C₂)Cl (4), La₂(C₂)Br (5), Ce₂(C₂)Br (6), Pr₂(C₂)Br (7), Ce₁₈(C₂)₉Cl₁₁ (8), and Ce₂₆(C₂)₁₃Cl₁₆ (9) were prepared by heating mixtures of LnX₃, Ln and carbon or in an alternatively way LnX₃, and “Ln₂C_3–x” in appropriate amounts for several days between 750 and 1200 °C. The crystal structures were investigated by X‐ray powder analysis (5–7) and/or single crystal diffraction (1–4, 8, 9). Pr₈(C₂)₄Cl₅ crystallizes in space group P2₁/c with the lattice parameters a = 7.6169(12), b = 16.689(2), c = 6.7688(2) Å, β = 103.94(1) °, Pr₁₄(C₂)₇Cl₉ in Pc with a = 7.6134(15), b = 29.432(6), c = 6.7705(14) Å, β = 104.00(3) °, Pr₂₂(C₂)₁₁Cl₁₄ in P2₁/c with a = 7.612(2), b = 46.127(9), c = 6.761(1) Å, β = 103.92(3) °, Ce₂(C₂)₂Cl in C2/c with a = 14.573(3), b = 4.129(1), c = 6.696(1) Å, β = 101.37(3) °, La₂(C₂)₂Br in C2/c with a = 15.313(5), b = 4.193(2), c = 6.842(2) Å, β = 100.53(3) °, Ce₂(C₂)₂Br in C2/c with a = 15.120(3), b = 4.179(1), c = 6.743(2) Å, β = 101.09(3) °, Pr₂(C₂)₂Br in C2/c with a = 15.054(5), b = 4.139(1), c = 6.713(3) Å, β = 101.08(3) °, Ce₁₈(C₂)₉Cl₁₁ in P$\bar{1}$ with a = 6.7705(14), b = 7.6573(15), c = 18.980(4) Å,α = 88.90(3) °, β = 80.32(3) °, γ = 76.09(3) °, and Ce₂₆(C₂)₁₃Cl₁₆ in P2₁/c with a = 7.6644(15), b = 54.249(11), c = 6.7956(14) Å, β = 103.98(3) ° The crystal structures are composed of Ln octahedra centered by C₂ dumbbells. Such Ln₆(C₂)‐octahedra are condensed into chains which are joined into undulated sheets. In compounds 1–4 three and four up and down inclined ribbons alternate (4₊4_–, 4₊3_–3₊4_–, 4₊4_–3₊4_–4₊3_–), in compounds 8 and 9 four and five (4₊5_–, 5₊4_–4₊5_–4₊4_–), and in compounds 4–7 one, one ribbons (1₊1_–) are present. The Ln‐(C₂)‐Ln layers are separated by monolayers of X atoms.     

Molecular mechanics study of the β-spiral conformations of the Phe4, Tyr4, and Trp4 analogs of elastomeric poly(Val1–Pro2–Gly3–Val4–Gly5)

The elastin-derived polypentapeptide, poly(VPGVG), and analogs are becoming model systems for protein as well as forming a new class of biomaterials. The β-spiral of poly(VPGVG) represents a new family of molecular structures in fibrous proteins. In particular for our interests here, aromatic amino acid residue substitutions at position four of poly(VPGVG) give rise to new polypeptides with interesting properties of increased elastic modulus, pressure sensitivity, etc. Molecular mechanics computations were carried out to answer the question, can the polypeptides with Phe, Tyr, and Trp substitution at position four of poly(VPGVG) form a β-spiral structure like poly(VPGVG)? Employed in this study was a combination of conformational search using ECEPP/2 and the build-up strategy and of molecular dynamics calculations using CHARMm. The results indicate that the VPGX Type II β-turn structure appears to be the most prominent secondary structural feature for the three aromatic residues containing polypentapeptides, although there is more evidence for VPGFG and VPGVG to assume the VPGVG-type structure than for VPGWG to do so. The study also shows that the aromatic side chains do not interrupt the β-spiral structure, even in the case of tryptophan.     

Two‐Dimensional Networks of [AuCl4]– and [AuBr4]– Anions

Several salts of protonated amines and aza‐aromatics with [AuCl₄]^– and [AuBr₄]^– anions contain two‐dimensional (“square”) anionic networks that display short halogen ··· halogen contacts. The Au₄ quadrilaterals formed by neighboring anions of the networks are to a good approximation squares, with sides of around 7.5 Å for tetrachloridoaurates and 8 Å for tetrabromidoaurates.     

[B(O–C6H4–CN)4]– based Silver and Copper Coordination Polymers

A series of new coordination polymers bearing the [B(O–C₆H₄–CN)₄]^– anion was synthesized. Two new, one dimensional coordination frameworks of the type M[B(O–C₆H₄–CN)₄] (M = Ag, Cu) were obtained by salt metathesis. The reactivity towards organic Lewis‐bases was studied. The reaction with bidentate ligands yielded two dimensional networks with the general formula [M(L)][B(O–C₆H₄–CN)₄] {L = 2,2′‐bipyridine, 4,4′‐bipyridine, 1,2‐bis(pyridyl)ethane, 1,4‐diazabicyclo[2.2.2]octane}. The synthesis, properties and single crystal structure are reported.