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Various iridium complexes consisting of phenylpyrazole (ppz) ligands and isoquinolinecarboxylic acids (iq) as ancillary ligands were designed by energy band-gap calculations via ab initio calculations and synthesized to give rise to various emission wavelengths as expected. Fine color tuning was achieved through varying the position of the methyl substituent on the phenylpyrazole moiety with HOMO electron densities. Additional color tuning was made possible by altering the LUMO through the use of different ancillary ligands such as 1-isoquinolinecarboxylic acid (1iq) and 3-isoquinolinecarboxylic acid (3iq).

C1-bridged and Me2Si-bridged 2,5-dimethylcylcopentadienyl ansa-zirconocene complexes, [Me(H)C(C5H4)(2,5-Me2C5H2)]ZrCl2 (6), [(CH3CH2CH2)(H)C(C5H4)(2,5-Me2C5H2)]ZrCl2 (9), [(Me)(H)C(2,5-Me2C5H2)2]ZrCl2 (13), and [Me2Si(2,5-Me2C5H2)2]ZrCl2 (15), are prepared by using 2-bromo-3-methoxy-2,5-dimethylcyclopentene (7) as a starting material. Solid structures of 6 and 13 were determined by X-ray crystallography. The C1-bridged zirconocene complexes 6, 9, and 13 are highly active for ethylene/norbornene copolymerization with high incorporation of norbornene, while the Me2Si-bridged complex 15 shows relatively low activity. Complex 9 shows the highest activity and the highest incorporation of norbornene among the complexes, but the molecular weight of the obtained polymer is relatively low.

The new organometallic compounds [{(E)-2-SC4H3CHCHC6H4-X-p}Ru(C6Me6)][CF3SO3]2 (X = MeO (1), Me (2), H (3), Br (4), NO2 (5)), bearing a (thiophene)Ru(C6Me6)2+ fragment in the end group, have been p...

The ferrocenyl bipyridines, 1,1'-bis(2-(4-pyridyl)vinyl)ferrocene (1a) and 1,1'-bis(2-(3-methyl-4- pyridyl)vinyl)ferrocene (1b), were cocrystallized with aromatic acids such as 4-alkoxybenzoic acids (2), terephthalic acid (3a), isophthalic acid (3b), phthalic acid (3c), and trimesic acid (4). Eight complexes were obtained as single crystals, and their crystal structures were successfully determined by X-ray analysis. When 1a was assembled with 2 ,a( 1+ 2) self-assembly occurred, to generate supramolecular arrays in which one molecule of 1a and two molecules of 2 were held together through hydrogen bonding. In the cocrystallization of ferrocenyl bipyridines with benzene dicarboxylic acid (3a, 3b, and 3c), proton transfer occurred depending on the kind of benzene dicarboxylic acid. Thus, the cocrystals of 1a + ‚3b - , 1b + ‚3b - , and 1b + ‚3c - consist of proton-transferred ionic supramolecular species, whereas that of 1b‚3a are composed of (2 + 2) assembled cyclic supramolecular structures. Complexation of 1a with 4 afforded the (2 + 3) self-assembly with an intriguing prismatic cagelike structure.

Deprotonation of the α-diimine compound {2,6-(CHMe2)2-C6H3}NC(CH3)C(CH3)N{2,6-(CHMe2)2-C6H3} with excess KH in THF gives dipotassium N,N‘-(1,2-dimethylene-1,2-ethanediyl)bis(2,6-diisopropylanilide) (1) in 75% yield. Reaction of 1 with bis(2-picolyl)zirconium dichloride generated in situ by the reaction of ZrCl4 and 2 equiv of (2-picolyl)potassium affords [N,N‘-(1,2-dimethylene-1,2-ethanediyl)bis(2,6-diisopropylanilido)-κ2N,N‘]bis(2-picolyl)zirconium(IV) (2) in 35% yield. Similar reaction of 1 with LMCl3 (L = Cp, Cp*; M = Zr, Hf) gives the desired complexes {2,6-(CHMe2)2-C6H3}NC(CH2)C(CH2)N{2,6-(CHMe2)2-C6H3}MLCl (L = Cp*, M = Zr, 4; L = Cp*, M = Hf, 5; L = Cp, M = Zr, 6) in 79%, 94% and 54% yields, respectively. Reaction of the chloride complexes with MeMgBr affords the corresponding methyl complexes {2,6-(CHMe2)2-C6H3}NC(CH2)C(CH2)N{2,6-(CHMe2)2-C6H3}MLMe (L = Cp*, M = Zr, 7; L = Cp*, M = Hf, 8; L = Cp, M = Zr, 9) in 63%, 69% and 90% yields, respectively. The solid-state structure of 7 was determined. Wh...

Reactions of ferrocenyl dipyridines (1a,b) with terephthalic (2) and trimesic acid (4) form [2+2] and [3+2] supramolecular assemblies 3 and 5, respectively. Crystallographic analyses reveal that they are stabilized by cooperative noncovalent interactions involving multiple hydrogen-bonding and π−π interactions.

Treatment of (arene)tricarbonylmanganese cations (arene = phenol, cresol) with nucleophiles affords η5-cyclohexadienyl complexes that can be demetalated to give ortho-substituted phenols. Acylation of the phenolic oxygen in the η5-cyclohexadienyl complexes obtained from phenol, followed by treatment with acid, gives manganese tricarbonyl cations with coordinated monosubstituted arenes. Reaction of η5-cyclohexadienyl complexes derived from ortho- and para-cresol with acid gives meta-substituted toluene manganese tricarbonyl cations, and those derived from meta-cresol give ortho- and/or para-substituted toluene manganese complexes depending upon the nucleophiles.

Employing pyrimidine-containing ligands such as 1-(4-pyridyl)-2-(4-pyrimydyl)ethene (L1) and 1-(4-pyridyl)-2-(3-methyl-4-pyridyl)ethene (L3) in assembly with Co(SCN)2 affords robust porous coordination polymers with uncoordinated nitrogen atoms on the channel walls.

Assemblies of 1-methyl-1',2-bis(4-pyridyl)ethene (mpe) and Co(NCS)(2) afford three isomeric framework networks and different topological features depending on the assembly conditions. Isomerism control and solid-to-solid transformation phenomena are observed among them.

Self-assembly between simple unsymmetrical ligands, such as 1-(3-pyridyl)-2-(4-pyridyl)ethene (L(1)) and 1-methyl-1'-(3-pyridyl)-2-(4-pyrimidyl)ethene (L(2)), and Co(NCS)(2) affords the unprecedented two-dimensional grid coordination polymers [Co(L(1))(2)(NCS)(2)](infinity) (1) and [Co(L(2))(2)(NCS)(2)](infinity) (2), respectively, with novel topological features which cannot be achieved using symmetrically bridging ligands.