Synthesis and crystal structure of (E)-2-benzyl-1,3-di-phenyl-iso-thio-uronium iodide.

In the title mol-ecular salt, C20H19N2S+·I-, prepared by the reaction of 1,3-di-phenyl-thio-urea and benzyl iodide, the C-S-C thio-ether bond angle is 101.66 (9)° and electrons are delocalized over the N+= C-N skeleton. The dihedral angle between the aromatic rings attached to the N atoms is 40.60 (9)°. In the crystal, N-H⋯I hydrogen bonds link the components into [100] chains.

Crystal structure of [3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne]nickel(II) diperchlorate.

The square-planar nickel(II) title complex, [Ni(C24H36F2N6)](ClO4)2 or [NiL](ClO4)2 (L = 3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne) was synthesized by a one-pot reaction of template condensation and its X-ray crystal structure was determined. The nickel(II) ion lies close by a twofold axis and the complex displays whole-mol-ecule disorder. Ligand L, a hexa-aza-cyclo-tetra-decane ring having 4-fluoro-phenethyl side chains attached to uncoordinated nitro-gen atoms, adopts a trans III (R,R,S,S) configuration. The average Ni-N bond distance is 1.934 (9) Å, which is quite similar to those of other nickel(II) complexes with similar ligands. The nickel(II) ion is located 0.051 (7) Šabove the least-squares plane through the four coordinated N atoms. The average C-N bond distance and C-N-C angle involving uncoordinated nitro-gen atoms are 1.425 (12) Šand 118.0 (9)°, respectively, indicating a significant contribution of sp 2 hybridization for these N atoms. The inter-molecular N-H⋯O, C-H⋯O/F hydrogen bonds of the complex form a network structure, which looks like a seamless floral lace pattern.

A Study of Phosphorescent Light Emitting Using Cyclometalated Pt(II) Complexes.

The reaction of platinum [Pt(4-(N,N-bis(piridyl)amino)stilbene)]Cl2 with 5,5"-(9,9-dioctyl-9H-fluorene- 2,7-diyl)di-2,2'-bipyridine, 2,2'-bipyridine, and 1,10-phenathroline affords the following complexes: [(4-(N,N-bis(piridyl)amino)stilbene)Pt(5,5"-(9,9-dioctyl-9H-fluorene-2,7-diyl)di-2,2'-bipyridine)] (1), [(4-(N,N-bis(piridyl)amino)stilbene)Pt(2,2'-bipyridine)] (2), and [(4-(N,N-bis(piridyl)amino)stilbene) Pt(1,10-phenathroline)] (3). In this study, new platinum complex compounds were synthesized utilizing the ligand of a 4-(N,N-bis(piridyl)amino)stilbene system. These complexes were analyzed using a 1H(13C)-NMR, UV-vis and PL spectrophotometer. The maximum wavelengths of complexes 1, 2, and 3 appear at 409 nm, 410 nm, and 503 nm, respectively. The quantum yields of these complexes are 0.32-0.92.

Preparation and Luminescent Property of the Self-Assembled Nanoscale Network Systems Combined Tetracyanoplatinate(II) and Copper(II)-Polyaza Complexes.

Complexes 1 and 2 were obtained by the reaction of [Cu(L1)](ClO4)2 (1) or [Cu(L2)](ClO4)2 (2) (L1 = 8-acetyl-1,3,6,8,10,13,15-heptaazatricyclo[13.1.1.113,15]octadecane, L2 = 3,7-bis(2-aminoethyl)- 1,3,5,7-tetraazabicyclo[3.3.l]decane) with K2[Pt(CN)4] in water. The X-ray crystal structures show that the geometry around Cu(II) ions of 1 and 2 adopts a square-pyramid. Their one-dimensional and two-dimensional structures are constructed by the intermolecular hydrogen bonding between the macrocyclic ligand and anionic complex ions or water molecules and Pt-Pt interaction. They show luminescent property and luminescence quantum yields are 0.341 and 0.187 for 1 and 2 in solid, respectively.

A synthetic study and characterization of the Pt(II) complexes with bipyridines back-born system.

The reaction of platinum [Pt(5,5-dmbpy)]Cl2 (5,5-dmbpy = 5,5'-dimethyl-2,2'-bipyridine) with 4,4'-dimethyl-2,2'-bipyridine (4,4-dmbpy), [Pt(dbbpy)]Cl2 (dbbpy = 4,4'-dibutyl-2,2'-bipyridine), [Pt(dpbpy)]Cl2 (dpbpy = 4,4'-dipentyl-2,2'-bipyridine) with 5,5'-dimethyl-2,2'-bipyridine (5,5-dmbpy) affords the following complexes: [(4,4-dmbpy)Pt(5,5-dmbpy)][PF6]2 (1) and [(dbbpy)Pt(5,5-dmbpy)][PF6]2 (2), [(dpbpy)Pt(5,5-dmbpy)][PF6]2 (3), [(5,5-dmbpy)Pt(5,5-dmbpy)][PF6]2 (4). This study was synthesized new platinum complex compounds utilizing ligand of 5,5'-Dimethyl-2,2'-dipyridyl System. To study the chemical composition was used 1H(13C)-NMR, UV-vis, Spectro photometer and Measurements about optical physics and chemical properties were measured to use spectrofluorometer. UV-vis absorption area was measured 310 nm to 383 nm and luminous wavelength was measured 390 nm to 419 nm.

(E)-2-Amino-4-(3,3-dimethyl-2-oxobutyl-idene)-1-[2-(2-hy-droxy-eth-oxy)eth-yl]-6-methyl-1,4-dihydro-pyridine-3-carbo-nitrile.

In the title compound, C(17)H(25)N(3)O(3), there are intra-molecular hydrogen bonds between an amine H atom and the ep-oxy O atom, and between a dihydro-pyridine ring H atom and the ketone O atom. In the crystal, mol-ecules are linked into a zigzag chain running parallel to the c axis by hydrogen bonds between the hy-droxy group and the ketone O atom. There are also weak C-H⋯O and C-H⋯π inter-actions which link the mol-ecules into sheets lying in the bc plane.

4,6-Di-tert-butyl-2,8-dimeth-oxy-dibenzo[b,d]furan.

In the title compound, C(22)H(28)O(3), the dihedral angle between the benzene rings is 3.47 (13)° and the five-membered furan ring is essentially planar with a largest deviation of 0.0052 (14) Å. The Csp(2)-Csp(2) bond length between the two benzene rings [1.443 (3) Å] is considerably shorter than those between the benzene and tertiary C atoms [1.538 (3) and 1.530 (3) Å], which are sp(2)-sp(3) hybridized. C-H⋯π inter-actions involving the furan and benzene rings are found in the crystal structure.

2-(2-Methyl-6-phenyl-1-propyl-1,4-dihydro-pyridin-4-yl-idene)propane-dinitrile.

In the title compound, C(18)H(17)N(3), the dihedral angle between the dihydropyridine and phenyl rings is 72.57 (5)° and that between the dihydropyridine ring and malononitrile plane is 5.19 (20)°. The C-C bond lengths in the pyridine ring are considerably shorter than those of normal single bonds, indicating that electrons on the dihydropyridine ring, including the non-bonding electrons of the N atom, are delocalized on the ring.

(E)-7-(4-Chloro-phen-yl)-5,7-dihydro-4H-pyrano[3,4-c]isoxazole-3-carbaldehyde oxime.

In the title compound, C(13)H(11)ClN(2)O(3), the nine-membered bicycle includes an oxime group having the C=N group in an E configuration. The isoxazole ring is almost planar [r.m.s. deviation = 0.0056 Å]; the dihedral angle between the isoxazole and 4-chloro-phenyl ring is 75.60 (5)°. In the crystal, inter-molecular O-H⋯N(isoxazole) hydrogen bonds give rise to chains running along the b axis.

Structure, magnetic and ion-exchange properties of self-assembled triaza-copper(II)-oxalate hybrides having nanoscale one-dimensional channel.

The X-ray structure, porous and magnetic property of a self-assembled network 1 is described in detail. The single crystal X-ray analysis provides 1 as a three-dimensional network, which contains two-dimensional permanent ring forming nanoscale one-dimensional channels. The inter-replacement of perchlorate and hexafluorophosphate anions in solid 1 proves its porous structure. There is somewhat strong antiferromagnetic interaction (J = -74.1 cm(-1)) between two copper(II) ions through oxalate bridge and weak antiferromagnetic interaction (J = -5.1 cm(-1) through AEP ligand.

Electronic coupling in dimetallic complexes with pi-conjugated bridge.

Compound 2, [(eta5-C5Me5) Fe(dppe)]2(mu-C[triple bond]C-CH==CH-C[triple bond]C), was prepared by the reaction of compound 1, [eta5-C5Me5) Fe(dppe)]2+ (mu2-C==CH-CH=CH-HC=C).(PF6)2-, with KOBu(t). Compound 2 showed two quasi-reversible one-electron oxidations at -0.674 and -0.253 V, respectively. The comproportionation constant, Kc, was calculated from these measurements. The mixed-valence(MV) radical cation 2+ showed an absorption peak at 1586 nm, which was assigned to the MV pi-pi band of the delocalized complex (Robin-Day Mixed-valence Class III) and the effective coupling parameter, Hab, is consistent with the presence of electronic delocalization.

Ligand Substitution Reactions at the Nickel of [Mo(3)NiS(4)(H(2)O)(10)](4+) with Two Water Soluble Phosphines, CO, Br(-), I(-), and NCS(-) and the Inertness of the 1,4,7-Triazacyclononane (L) Complex [Mo(3)(NiL)S(4)(H(2)O)(9)](4+).

Comparisons (25 degrees C) are made of substitution reactions, X replacing H(2)O, at the tetrahedral Ni of the heterometallic sulfido cuboidal cluster [Mo(3)NiS(4)(H(2)O)(10)](4+), I = 2.00 M (LiClO(4)). Stopped-flow formation rate constants (k(f)/M(-)(1) s(-)(1)) for six X reagents, including two water soluble air-stable phosphines, 1,3,5-triaza-7-phosphaadamantane PTA (119) and tris(3-sulfonatophenyl)phosphine TPPTS(3)(-) (58), and CO (0.66), Br(-) (14.6), I(-) (32.3), and NCS(-) (44) are reported alongside the previous value for Cl(-) (9.4). A dependence on [H(+)] is observed with PTA, which gives an unreactive form confirmed by NMR as N-protonated PTA (acid dissociation constant K(a) = 0.61 M), but in no other cases with [H(+)] in the range 0.30-2.00 M. The narrow spread of rate constants for all but the CO reaction is consistent with an I(d) dissociative interchange mechanism. In addition NMR studies with H(2)(17)O enriched solvent are too slow for direct determination of the water-exchange rate constant indicating a value <10(3) s(-)(1). Equilibrium constants/M(-)(1) for 1:1 complexing with the different X groups at the Ni are obtained for PTA (2040) and TPPTS(3)(-) (8900) by direct spectrophotometry and from kinetic studies (k(f)/k(b)) for Cl(-) (97), Br(-) (150), NCS(-) (690), and CO (5150). No NCS(-) substitution at the Ni is observed in the case of the heterometallic cube [Mo(3)Ni(L)S(4)(H(2)O)(9)](4+), with tridentate 1,4,7-triazacyclononane(L) coordinated to the Ni. Substitution of NCS(-) for H(2)O, at the Mo's of [Mo(3)NiS(4)(H(2)O)(10)](4+) and [Mo(3)(NiL)S(4)(H(2)O)(9)](4+) are much slower secondary processes, with k(f) = 2.7 x 10(-)(4) M(-)(1) s(-)(1) and 0.94 x 10(-)(4) M(-)(1) s(-)(1) respectively. No substitution of H(2)O by TPPTS(3)(-) or CO is observed over approximately 1h at either metal on [Mo(3)FeS(4)(H(2)O)(10)](4+), on [Mo(4)S(4)(H(2)O)(12)](5+) or [Mo(3)S(4)(H(2)O)(9)](4+).