Cu(I) and Ag(I) complexes of 7-azaindolyl and 2,2'-dipyridylamino substituted 1,3,5-triazine and benzene: the central core impact on structure, solution dynamics and fluorescence of the complexes.

The interactions of Cu(i) and Ag(i) ions with four star-shaped ligands, 2,4,6-tris(N-7-azaindolyl)-1,3,5-triazine (tat), 1,3,5-tris(N-7-azaindolyl)benzene (tab), 2,4,6-tris(2,2'-dipyridylamino)-1,3,5-triazine (tdat) and 1,3,5-tris(2,2'-dipyridylamino)benzene (tdab) have been investigated by X-ray diffraction, NMR and fluorescent spectroscopic analyses. Eight new complexes [Cu(PPh(3))(tat)][BF(4)] (), [Cu(PPh(3))(tab)][BF(4)] (), [Cu(PPh(3))(tdab)][BF(4)] (), {[Cu(PPh(3))(2)](2)(tdat)]}[BF(4)](2) (), (AgNO(3))(1.5)(tab) (), (AgNO(3))(2)(tat) (), (AgNO(3))(4)(tdab) (), and (AgNO(3))(3)(tdat)(H(2)O)(2) () have been isolated from the reactions of [Cu(PPh(3))(2)(CH(3)CN)(2)][BF(4)] and AgNO(3) with the corresponding ligands.

Sequential formation of yellow, red, and orange 1-phenyl-3,3-biphenylene-allene dimers prior to blue tetracene formation: Helicity reversal in trans-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane.

1-Phenyl-3,3-biphenyleneallene (2), the base-catalyzed rearrangement product of 9-phenylethynylfluorene (1) yields a yellow, head-to-tail dimer 6 that, upon gentle warming, is converted to the red tail-to-tail isomer trans-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane (7), in which the two fluorenylidene moieties severely overlap. The helical sense of the fluorenylidene moieties in 7 matches that of the phenyl substituents, and the interplanar angle between the fluorenylidene moieties is 41 degrees . At 80 degrees C, 6 isomerizes to orange cis-3,4-diphenyl-1,2-bis(fluorenylidene)cyclobutane (8), which at 110 degrees C is converted to orange trans diastereomer 9, whereby the helicity of the overlapping fluorenylidene moieties is reversed from that in 7 such that they are aligned with the ring hydrogen atoms, and the interplanar angle between the fluorenylidene moieties is now 60 degrees .

Three-coordinate organoboron compounds BAr2R (Ar = mesityl, R = 7-azaindolyl- or 2,2'-dipyridylamino-functionalized aryl or thienyl) for electroluminescent devices and supramolecular assembly.

Eight novel three-coordinate boron compounds with the general formula BAr(2)L, in which Ar is mesityl and L is a 7-azaindolyl- or a 2,2'-dipyridylamino-functionalized aryl or thienyl ligand, have been synthesized by Suzuki coupling, Ullmann condensation methods, or simple substitution reactions (L = p-(2,2'-dipyridylamino)phenyl, 1; p-(2,2'-dipyridylamino)biphenyl, 2; p-(7-azaindolyl)phenyl, 3; p-(7-azaindolyl)biphenyl, 4; 3,5-bis(2,2'-dipyridylamino)phenyl, 5; 3,5-bis(7-azaindolyl)phenyl, 6; p-[3,5-bis(2,2'-dipyridylamino)phenyl]phenyl, 7; 5-[p-(2,2'-dipyridylamino)phenyl]-2-thienyl, 8). The structures of 1, 3, and 5-7 have been determined by X-ray diffraction analyses. These new boron compounds are bright blue emitters.

Palladium(II) complexes of bowls, pinwheels, cages, and N,C,N-pincers of starburst ligands 1,3,5-Tris(di-2-pyridylamino)benzene and 2,4,6-Tris(di-2-pyridylamino)-1,3,5-triazene.

The reactions of Pd(II) ions with starburst ligands 1,3,5-tris(di-2-pyridylamino)benzene (tdab) and 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazene (tdat) have been investigated. Complexes with the Pd:tdab (or tdat) ratio being 1:1 and 3:1 have been isolated and characterized. The structures of five new Pd(II) complexes containing the starburst ligands have been determined by X-ray diffraction analyses, which include chelate compounds [PdCl(2)(tdab)], 1, [(PdCl(2))(3)(tdab)], 2, [(Pd(OAc)(2))(3)(tdab)], 4, and [(Pd(OAc)(2))(3)(tdat)], 5, and a cyclometalated compound [Pd(OAc)(NCN-tdab)], 3.

Blue luminescent rigid molecular rods bearing N-7-azaindolyl and 2,2'-dipyridylamino and their Zn(II) and Ag(I) complexes.

To investigate the luminescent and thermal properties of organic compounds with rigid entities, a series of new blue/purple luminescent bridging ligands, 4,4'-(N-7-azaindolyl)diphenylacetylene (5), 4-(N-7-azaindolyl)-4'-(2,2'-dipyridylamino)diphenylacetylene (6), 4,4'-(2,2'-dipyridylamino)diphenylacetylene (7), and 4,4'-(dipyridylamino)diphenylbutadiyne (8) have been synthesized through Pd-mediated Sonogashira coupling. The structures of compounds 6 and 8 were determined by single-crystal X-ray diffraction analyses. Compounds 5-8 are luminescent in solution at room temperature, with emission lambda(max) = 361, 382, 386, and 405 nm, respectively.

Anion dependent structures of luminescent silver(i) complexes.

The reaction of AgX, where X = trifluoroacetate (CF(3)CO(2)(-), tfa), nitrate (NO(3)(-)), trifluoromethanesulfonate (triflate, CF(3)SO(3)(-), OTf), hexafluorophosphate (PF(6)(-)), or perchlorate (ClO(4)(-)), with 2,2',3' '-tripyridylamine (tpa) yields five novel silver(I) complexes, which have been structurally characterized. The five complexes have the same 1:1 stoichiometry of Ag/tpa but exhibit different modes of coordination, depending upon the counterion present in the compound. Compound 1, [Ag(tpa)(tfa)](n)(), forms a 1D coordination polymer of [Ag(tpa)(tfa)](2) dimer units linked through bridging tfa counterions.

Syntheses, structures, and electroluminescence of Ln(2)(acac-azain)(4)(mu-acac-azain)(2) [acac-azain = 1-(N-7-azaindolyl)-1,3-butanedionato, Ln = Tb(III) and Y(III)].

Two new luminescent lanthanide complexes Ln(2)(acac-azain)(4)(mu-acac-azain)(2) [acac-azain = 1-(N-7-azaindolyl)-1,3-butanedionato, Ln = Tb(III), 1, Y(III), 2] have been synthesized and structurally characterized. These two dinuclear complexes are isostructural with the two lanthanide ions being bridged by two acac-azain ligands. Each of the two metal ions is further chelated by four oxygen atoms from two acac-azain ligands, resulting in a coordination number eight for each metal ion.

A Blue Luminescent Star-Shaped Zn Complex that Can Detect Benzene.

Binding benzene: A novel blue luminescent star-shaped Zn complex has been found to be able to detect benzene selectively by fluorescent quenching. This is attributed to the compoundapos;s high affinity to benzene, as demonstrated in the crystal structure (see picture; yellow: benzene, red: zinc).

Helical Coordination Polymers with Large Chiral Cavities.

A quarter of the unit cell volume of [{Ni(4,4'-dipy)(3-nitrobenzoate) (MeOH) } ], which crystallizes in the form of helices, is occupied by large chiral cavities (400-500 Å ). The cavities are capable of encapsulating not only single molecules, but also face-to-face dimers of nitrobenzene (see stick model). 4,4'-dipy=4,4'-bipyridine.