Crystal Structures Of 1a Research Articles

Reaction of dimethylplatinum(II) complexes with PhCH2CH2Br: Comparative reactivity with CH3CH2Br and PhCH2Br and synthesis of Pt(IV) complexes

Oxidative addition of 2‐phenylethylbromide (PhCH2CH2Br) to dimethylplatinum(II) complexes [PtMe2(NN)] (1a, NN = 2,2′‐bipyridine (bpy); 1b, NN = 1,10‐phenanthroline (phen)) afforded the new organoplatinum(IV) complexes [PtMe2(Br)(PhCH2CH2)(bpy)], as a mixture of trans (2a) and cis (3a) isomers, and [PtMe2(Br)(PhCH2CH2)(phen)], as a mixture of trans (2b) and cis (3b) isomers, respectively. The new Pt(IV) complexes were readily characterized using multinuclear (1H and 13C) NMR spectroscopy and elemental microanalysis. The crystal structure of 2a was further determined using X‐ray crystallography indicating an octahedral geometry around the platinum centre. A comparison of reactivity of RCH2Br reagents (R = CH3, Ph or PhCH2) in their oxidative addition reactions with complex 1a, with an emphasis on the effects of the R groups of alkyl halides, was also conducted using density functional theory.

Unexpected simultaneous synthesis of trisubstituted quinolines and acylhydrazones under catalyst-free conditions

ABSTRACTTrisubstituted quinolines and acylhydrazones were unexpectedly prepared from a reaction of N′-((2-aminophenyl)(phenyl)methylene)benzohydrazides with acetylenic esters. Using of N′-((2-aminophenyl)(phenyl)methylene)benzohydrazides led to obtain not only quinoline, but also a second pharmaceutical important product acylhydrazone. Notably, excellent yields, operational simplicity, short reaction times, and the avoidance of the use of catalysts make this approach an attractive complementary method to produce quinoline-2,3-dicarboxylates. The crystal structure of 5a was determined using single-crystal X-ray crystallography. The results showed that crystal packing diagram of 5a is of two pairs of molecules that have two independent alternate intermolecular 1D-polymeric H-bonds between two perpendicular molecules.

Ferrocenyl thiocarboxylates: Synthesis, solid-state structure and electrochemical investigations

The synthesis and characterization of four ferrocenyl thiocarboxylate complexes are reported. Thus, treatment of [Fe(η5-C5H5)(η5-C5H4S−)] (1) with one equivalent of the acid chlorides 2-ClC(O)-cC4H3X(2a, X = O; 2b, X = NMe) gave [Fe(η5-C5H5)(η5-C5H4SC(O)-2-cC4H3X)] (3a, X = O; 3b, X = NMe (b)). When 1,1′-[Fe(η5-C5H4S−)2] (4) was reacted with 2-ClC(O)-cC4H3X in a 1:2 molar ratio then the respective ferrocenyl-1,1'-bis(thiocarboxylates) 1,1′-[Fe(η5-C5H4SC(O)-2-cC4H3X)2] (5a, X = O; 5b, X = NMe (b)) were produced. The solid state structures of 5a and 5b were determined by X-ray crystal structure analysis. The Crystal structure of 5a indicated the presence of oxygen…oxygen contacts, the inter-oxygen distance is 0.13 Å less than the sum of van der Waals radii. Investigation of Cambridge Structural Data base for 2-substtiuted furan molecules indicated the presence of short O…O contacts in 49 examples. Geometrical analysis of the O…O contacts indicated that the geometrical arrangement of these contacts is very similar to the well-defined C-X…X-C contacts (X = Cl, Br or I). Cyclic voltammetric studies of 3a, b and 5a, b showed reversible events at 158 and 243 mV for 3a, b and at 187 and 284 mV for 5a, b, using [NnBu4][B(C6F5)4] as the supporting electrolyte. It was found that the furyl-functionalized systems resulted in a significant higher Fc/Fc+ redox potential (E0′) as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc+ redox potential (E0′) for 5a, b is significantly higher than the one for 3a, b, due to the presence of two electron withdrawing thioester groups attached to the ferrocene in 5a, b.

The effect of an ancillary ligand proton on the photophysical properties of some RuIIN6cores: a proton valve

The proton of the ancillary ligand (lig) in [Ru(bpy/phen)2(lig)]2+decides whether a Ru(ii)N6core will be emissive or not.

Syntheses, Structural Studies, and Copper Iodide Complexes of Macrocycles Derived from Williamson Ether Syntheses Involving 2,9-Bis(4-hydroxyphenyl)-1,10-phenanthroline, α,ω-Dibromides, and Resorcinol or 2,7-Dihydroxynaphthalene

1,3-Bis(6-bromohexyloxy)benzene, 2,7-bis(6-bromohexyloxy)naphthalene, 1,3-bis(4-bromomethylbenzyloxy)benzene, and 1,3-bis(3-bromomethylbenzyloxy)benzene were prepared via Williamson ether synthesis using resorcinol or 2,7-dihydroxynaphthalene and 1,6-dibromohexane, 1,4-bis(bromomethyl)benzene, or 1,3-bis(bromomethyl)benzene (21–47 % yield). These dibromides were condensed with 2,9-bis(4-hydroxyphenyl)-1,10-phenanthroline in the presence of K2CO3 to give the corresponding 31- to 35-membered macrocycles (3a–d, 22–63 % yield). When 3a–d were treated with CuI, mononuclear 1 : 1 complexes formed, in which the CuI chelates to the nitrogen donor atoms of the phenanthroline moiety (4a–d, 40–80 % yield). The crystal structures of 3a–c and 4a–c were determined and analyzed using density functional theory calculations and in the context of rotaxanes that could be formed by treatment of 4a–d with terminal alkynes (e.g. macrocycle dimensions, void volumes). The copper and iodide atoms in 4a–c significantly protrude from the least-squares plane of the phenanthroline moiety (0.46–0.63 Å and 1.65–2.07 Å).

A copper(II) complex of benzimidazole-based ligand: synthesis, structure, redox aspects and fluorescence properties

Employing 1-(2-methoxybenzyl)-2-(2-methoxyphenyl)-1H-benzimidazole (bpb) as a monodentate ligand, a new greenish-blue copper(II) complex, [Cu(bpb)2(NO3)2] (1a), has been synthesized. 1a has been characterized analytically and spectroscopically. The X-ray crystal structure of 1a reveals that it adopts a cis disposition with respect to the ligands. The solid state structure of 1a is stabilized by intramolecular offset face-to-face π–π stacking. Non-covalent supramolecular edge-to-face C–H⋯π interactions with neighboring molecules give 1-D supramolecular chains that further lead to the formation of an assembled 3-D supramolecular metal-organic framework via hydrogen bonding interactions. 1a shows blue fluorescence most likely due to intramolecular offset face-to-face π–π stacking. At room temperature, 1a is one-electron paramagnetic. It shows a rhombic EPR spectrum with g1 = 2.12, g2 = 2.42, and g3 = 2.52 in the solid state at liquid nitrogen temperature. In cyclic voltammetry, 1a displays a one-electron oxidative Cu(II)/Cu(III) couple. Our DFT calculations, corroborate the observed experimental results of 1a.

Nickel Complexes of Pyridine‐Functionalized N‐Heterocyclic Carbenes: Syntheses, Structures, and Activity in Electrocatalytic Hydrogen Production

Two bis(benz)imidazolium salts alkylated with pyridyl side arms, H2L1Br2 (1,2‐bis{[1‐(2‐pyridylmethyl)benzimidazolium‐3‐yl]methyl}benzene bromide) and H2L2Br2 (1,2‐bis{[1‐(2‐pyridylmethyl)imidazolium‐3‐yl]methyl}benzene bromide) have been prepared and were used as precursors in the synthesis of novel nickel compounds of N‐heterocyclic carbenes (Ni‐NHCs). The four Ni‐NHC complexes [Ni(L1)Br]Br (1a), [Ni(L1)](PF6)2 (1b), [Ni(L2)]Br2 (2a) and [Ni(L2)](PF6)2 (2b) were isolated and characterized by various methods, and the X‐ray crystal structures of 1a, 2a and 2b are reported. The nickel ion in 1a is in a square‐pyramidal geometry with one of the bromide ions in the apical position, the nickel ions in 2a and 2b are in square‐planar geometries. The compounds of the ligand with an imidazole‐based carbene revealed much higher activity in electrocatalytic proton reduction and better acid tolerance, although their overpotentials are higher than those of the benzimidazole‐based compounds. The presence of bromide ions has an adverse effect on the redox potentials as well as the overpotentials for proton reduction. Complex 2b, having the most planar coordination geometry, appeared to have the highest catalytic efficiency for proton reduction in DMF (ic/ip = 50, kobs = 490 s–1 at 0.1 V/s) when using acetic acid as the proton source. To the best of our knowledge, this is the first report of Ni‐NHC complexes that are active in electrocatalytic proton reduction.

Syntheses, Reactivity, Structures, and Dynamic Properties of Gyroscope-like Iron Carbonyl Complexes Based on Dibridgehead Diarsine Cages

Reactions of BrMg(CH2)mCH═CH2 (m = 4, a; 5, b; 6, c) and AsCl3 (0.30 equiv) give the arsines As((CH2)mCH═CH2)3 (58–70%), which when added to iron tricarbonyl sources yield trans-Fe(CO)3(As((CH2)mCH═CH2)3)2 (66–70%). Reactions with Grubbs’ catalyst (18 mol %, CH2Cl2, reflux) and then hydrogenations (ClRh(PPh3)3/60–80 °C) afford gyroscope-like complexes trans-Fe(CO)3(As((CH2)n)3As) (4a–c, n = 2m + 2; 41–59%/two steps) of idealized D3h symmetry. Additions of NO+BF4– give the isoelectronic and isosteric cations [Fe(CO)2(NO)(As((CH2)n)3As)]+BF4– (5a–c+ BF4–; 81–98%), and [H(OEt2)2]+BArf– (BArf = B(3,5-C6H3(CF3)2)4) gives the hydride complexes mer,trans-[Fe(CO)3(H)(As((CH2)n)3As)]+BArf– (6a–c+ BArf–; 98–99%). Crystal structures of 4a–c and 5b+BF4– are determined. That of 4c suggests enough van der Waals clearance for the Fe(CO)3 moiety to rotate within the As(CH2)14As linkages; that of 4a shows rotation to be blocked by the shorter As(CH2)10As linkages. The rotator dynamics in these complexes are probed by VT N...

Formation of Ternary Inclusion Crystal and Enantioseparation of Alkyl Aryl Sulfoxides by the Salt of Urea-Modified l-Phenylalanine and an Achiral Amine

Chiral supramolecular hosts comprising urea-modified l-phenylalanines and achiral primary amines were developed, which facilitated enantioselective inclusion of alkyl aryl sulfoxides (3) up to 89% ee owing to the formation of ternary inclusion crystals. From the structural optimization of the components, the combination of N-(phenylcarbamoyl)-l-phenylalanine (1a) and benzhydrylamine (2e) showed the best inclusion ability among the considered supramolecular hosts. The type of the hydrogen-bonding network of ammonium-carboxylate salts 1a·2 was dependent on the steric bulk of combined primary amine 2. The rigid phenylurea moiety of 1a and moderate steric bulk of 2e played an important role in their high inclusion ability. Host 1a·2e afforded two ternary polymorphic inclusion crystals with the inclusion of acetonitrile. Furthermore, the crystal structures of 1a·2e·3 revealed that the inclusion of 3 was assisted by hydrogen bonding to the host and that stereoselectivity reversal occurred for larger sulfoxides, which was attributed to packing variations of one-dimensional hydrogen-bonding networks.

Cobalt(II) and nickel(II) complexes with N-benzyl- and N-(p-nitrobenzyl)iminodiacetic acids. Structural and vibrational spectroscopic characterization and DFT study

The reactions of N-benzyliminodiacetic acid (BnidaH2) and N-(para-nitrobenzyl)iminodiacetic acid (p-NO2BnidaH2) with cobalt(II) and nickel(II) acetate in aqueous solutions were performed. Three new complexes [Co(Bnida)(H2O)3]·H2O (1a·H2O), [Co(p-NO2Bnida)(H2O)3]·½H2O (2a·½H2O) and [Ni(p-NO2Bnida)(H2O)3]·½H2O (2b·½H2O) were prepared and characterized by infrared spectroscopy and thermal analysis (TG/DTA). The molecular and crystal structures of 1a·H2O and 2b·½H2O were determined by X-ray crystallography. The octahedral coordination environments around the Co(II) ion in 1a and Ni(II) ion in 2b consist of an O,N,O′-tridentate N-arylalkyliminodiacetate ion and three water molecules, resulting in the formation of fac-isomers in both cases. The molecular geometry and infrared spectra of these three complexes, together with previously synthesized and characterized complex [Ni(Bnida)(H2O)3]·H2O (1b·H2O) are studied by DFT calculations using BP86/6-311G(d,p) and mPW1PW91/6-311G(d,p) computational model.

C-H Activation in Primary 3-Phenylpropylamines: Synthesis of Seven-Membered Palladacycles through Orthometalation. Stoichiometric Preparation of Benzazepinones and Catalytic Synthesis of Ureas.

The dimeric cyclometalated complexes [Pd2{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}2(μ-Cl)2] (R = Me (1a), H (1b)) are prepared by reacting 1,1-dimethyl-3-phenylpropylammonium or 1-methyl-3-phenylpropylammonium triflate with Pd(OAc)2 in a 1:1 molar ratio and subsequent treatment with excess NaCl. The mononuclear derivatives [Pd{κ(2)C,N-C6H4CH2CH2C(R)(Me)NH2-2}Cl(L)] (L = PPh3, R = Me (3a), H (3b); L = 4-picoline (4-pic), R = Me (4a), H (4b)) were prepared from 1a,b by splitting the chloro bridges with the neutral ligands L. A conformational analysis of the mononuclear palladacycles in solution has been carried out. Insertion of CO takes place into the Pd-C bond of complexes 1a,b, affording Pd(0) and the tetrahydro-benzazepinone 5a or 5b, which possesses potential pharmacological interest. Additionally, the triflate salt A or B undergoes catalytic carbonylation with CO to afford the corresponding N,N'-dialkylurea, using Pd(OAc)2/Cu(OAc)2, in boiling acetonitrile. The crystal structures of 3a·(1)/2H2O, 3b, 4b·CHCl3, and 5a were determined by X-ray diffraction studies.

Synthesis and structural characterization of ferrocene phosphines modified with polar pendants and their palladium(II) complexes. Part I: N-aminocarbonyl and N-acyl phosphinoferrocene carboxamides

Acylation of 1′-(diphenylphosphino)-1-(aminocarbonyl)ferrocene, Ph2PfcCONH2 (1; fc = ferrocene-1,1′-diyl), afforded a series of acyl-ureas including Ph2PfcCONHCONHEt (1a), Ph2PfcCONHCONHPh (1b), and Ph2PfcCONHCONMe2 (1c) as well as the acetyl derivative Ph2PfcCONHAc (1d). Compounds 1a-d were converted to the corresponding phosphine oxides (2a-d) and further examined as ligands in Pd(II) complexes. The reactions of 1a-d with [PdCl2(cod)] (cod = cycloocta-1,5-diene) at a 2:1 ligand-to-metal ratio gave the bis(phosphine) complexes [PdCl2(L-κP)2] (3a-d; L = 1a-d), whereas the reactions with [Pd(LNC)Cl]2 (LNC = [2-(dimethylamino-κN)methyl]phenyl-κC1) produced the bridge-cleavage products, [PdCl(LNC)(L-κP)] (4a-d). Removal of the Pd-bound halide from 4a-d with Ag[SbF6] furnished the corresponding cationic bis-chelate complexes [Pd(LNC)(L-κ2O,P)][SbF6] (5a-d). All compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and elemental analysis. The crystal structures of 1a, 2a-c, 3a·2CHCl3, 3b·2CHCl3, 3d·2CHCl3, 4a·3CHCl3, 4b·2.5CHCl3, 5a·CHCl3, 5b·2CH2Cl2, and 5d were determined by single-crystal X-ray diffraction analysis, which revealed that the hydrogen-bonded arrays formed in the crystals of free ligands are often preserved in the structures of their complexes.

Synthesis of New 3‐(Furan‐2‐yl)‐Substituted Dibenzo‐Diazepin‐1‐one Derivatives

A new series of 3‐(furan‐2‐yl) dibenzo‐diazepin‐1‐one derivatives were synthesized by condensation of 5‐(furan‐2‐yl)‐1,3‐cyclohexanedione, o‐phenylenediamine, and aromatic aldehydes, in which in some of them existed two very close isomer compounds. All the compounds were characterized by IR, MS, 1H NMR, and elemental analysis. Also presented were the crystal structures of 3a, 3b and 3e, which were obtained and determined by X‐ray single‐crystal diffraction.

Synthesis of two nickel (II) complexes bearing pyrrolide-imine ligand and their catalytic effects on thermal decomposition of ammonium perchlorate

Two pyrrolide-imine chelating Ni(II) complexes {[2-(2-CH3O-C6H4-NCH)C4H3N]2Ni (2a) and [(Fc-NCH)]C4H3N]2Ni (2b, Fc=ferrocenyl)} were prepared via treating corresponding Schiff base with 0.5 equiv. NiCl2·6H2O in moderate yields. The crystal structures of 2a and 2b were determined by single-crystal X-ray diffraction. Atom Ni(II) of 2a was coordinated by two pyrrolide-imine ligands in trans position to display a twisted octahedral coordination geometry. Ni(II) of 2b had a distorted square-planar geometry, bonded with two ferrocenyl pyrrole-imine ligands, each ferrocene and pyrrole of ligands adopting a trans conformation. The UV–vis spectroscopy and electrochemical measurements were investigated. The catalytic efficiency of the complexes on the thermal decomposition of ammonium perchlorate (AP) was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Compared with the thermal decomposition of pure AP, the decomposition temperatures were decreased by 27°C, 77°C, 88°C and 172°C, respectively when 1a, 1b, 2a and 2b were added in AP. The results indicated that the Ni(II) complex 2b bearing ferrocene-based pyrrolide-imine N,N-chelate ligand displayed an excellent catalytic efficiency on the thermal decomposition of AP.

Spin crossover in tetranuclear Fe(II) complexes, {[(tpma)Fe(μ-CN)]4}X4 (X = ClO4(-), BF4(-)).

Two Fe(II) complexes, {[(tpma)Fe(μ-CN)]4}X4 (X = ClO4(-) (1a), BF4(-) (1b); tpma = tris(2-pyridylmethyl)amine), were prepared by reacting the {Fe(tpma)}(2+) building block with (Bu4N)CN. The crystal structures of 1a and 1b feature a tetranuclear cation composed of cyanide-bridged Fe(II) ions, each capped with a tetradentate tpma ligand. The Fe4(μ-CN)4 core of the complex is strongly distorted, assuming a butterfly-like geometry. Both complexes exhibit gradual temperature-driven spin crossover (SCO) associated with the high-spin (HS) ↔ low-spin (LS) transition at two out of four metal centers. The evolution of HS and LS Fe(II) ions with temperature was followed by a combination of X-ray crystallography, magnetic measurements, and Mössbauer spectroscopy. Only the Fe(II) ions surrounded by six N atoms undergo the SCO. A comparison of the temperature-dependent SCO curves for the samples stored under solvent and the dried samples shows that the former exhibit a much more abrupt SCO. This finding was interpreted in terms of the increased structural disorder and decreased crystallinity caused by the loss of the interstitial solvent molecules in the dried samples.

Palladacycle from Cyclometalation of the Unsubstituted Cyclopentadienyl Ring in Ferrocene: Synthesis, Characterization, Theoretical Studies, and Application to Suzuki–Miyaura Reaction

The ferrocenylimines of general formula [(η5-C5H5)Fe(η5-C5H4)-CH2N═CH-C(R)═CH-C6H5] with R = H (2a) and CH3 (2b) were conveniently prepared from ferrocenylmethylamine. Reaction of 2a,b with lithium tetrachloropalladate in methanol in the presence of anhydrous sodium acetate resulted in the formation of the di-μ-chloro-bridged heteroannular cyclopalladated complexes 3a,b via the unsubstituted ferrocenyl C–H bond activation of the related ligands. Treatment of 3a,b with triphenylphosphine gave Pd{[(η5-C5H4)Fe(η5-C5H4)CH2N═CH-CH═CH-C6H5]}ClPPh3 (4a) and Pd{[(η5-C5H4)Fe(η5-C5H4)-CH2N═CH-C(CH3)═CH-C6H5]}ClPPh3 (4b), respectively. The crystal structures of 4a,b confirmed the formation of a carbon–palladium bond by using a carbon atom in the unsubstituted cyclopentadienyl ring. Additionally, theoretical studies using density functional theory calculations were carried out in order to account for the regioselectivity of cyclometalation. As for the catalysts, using 0.1% of palladacycles 4a,b in the presence of K3P...

Deep-red phosphorescent iridium(III) complexes containing 1-(benzo[b] thiophen-2-yl) isoquinoline ligand: synthesis, photophysical and electrochemical properties and DFT calculations.

Four new bis-cyclometalated iridium(III) complexes, [Ir(btq) 2phen] [PF6] (3a), [Ir(btq) 2bpy] [PF6] (3b), [Ir(btq) 2dtbipy] [PF6] (3c) and [Ir(btq) 2pic] (3d) (btq = 1-(benzo[b] thiophen-2-yl) isoquinoline, phen = 1,10-phenanthroline, bpy = 2,2'-bipyridine, dtbipy = 4,4'-di-tert-butyl-2,2'-bipyridine, pic = picolinic acid) have been synthesized and fully characterized. The crystal structure of 3a has been determined by X-ray analysis. The photophysical and electrochemical properties of these new complexes 3a - 3d have been studied. The photoluminescence spectra of all Ir(III) complexes exhibit deep-red emission maxima at 682, 682, 683 and 698nm, respectively. The most representative molecular orbital energy-level diagrams and the lowest energy electronic transitions of 3a - 3d have been calculated with density functional theory (DFT) and time-dependent DFT (TD - DFT). The results show that the pic ancillary ligand of complex 3d influences the absorption and emission energies with a further red-shift relative to other three complexes 3a - 3c.

A new trans-dioxorhenium(V) complex with 4-aminopyridine: synthesis, structure, electrochemical aspects, DFT, and TD-DFT calculations

The reaction of 1 : 4.4 M proportion of cis-[ReO2I(PPh3)2] and 4-aminopyridine (ampy) in acetone–water gives trans-[ReO2(ampy)4]I·2H2O (1a) in 85% yield. 1a has been characterized by C, H, and N microanalyses, FT-IR, UV–vis, 1H NMR spectroscopy, and molar conductivity. The X-ray crystal structure of 1a reveals an octahedral trans dioxorhenium(V) complex with a “N4O2” coordination for rhenium. 1a has an orthorhombic space group C2221 with a = 17.576(4), b = 19.370(4), c = 15.730(4) Å, V = 5355(2) Å3, and Z = 8. Geometry optimization of the trans-O,O complex, 1a and its cis-O,O analog, 1b performed at the level of density functional theory reveal that 1a is more stable than 1b by 25 kcal M–1 in the gas phase. The electronic spectrum of 1a was also analyzed at the level of time-dependent density functional theory. Excitation of 1a in methanol at 450 nm leads to a fluorescent emission at 505 nm with a quantum yield (Ф) of 0.04. Electrochemical studies of 1a in acetonitrile show a quasi-reversible Re(V) to Re(VI) oxidation at 0.618 V versus Ag/AgCl. This redox potential matches with the calculated redox potential of 0.621 V versus Ag/AgCl.

Ferrocene-based sulfonyl dihydropyrazole derivatives: Synthesis, structure, electrochemistry and effect on thermal decomposition of NH4ClO4

Three ferrocene-based sulfonyl-substituted dihydropyrazoles 3a–c have been synthesized, from the corresponding α,β-unsaturated diketones, and fully characterized. The crystal structures of 3a–c have been confirmed by X-ray crystallography, and electrochemistry behaviors of 3a–c have been examined by cyclic voltammetry (CV). Representatively, the mechanism of the electron transfer in redox process of 3a has been verified by density functional theory (DFT) calculation. It has been found that the activity of catalytic decomposition of ammonium perchlorate (AP) is significantly lowered (by 62.9–104.7°C) with an addition of 3a–c. We expect that the ferrocene-based sulfonyl dihydropyrazole derivatives would have a great value in burning rate catalyst as composite solid propellants.

Four new cyclometalated phenylisoquinoline-based Ir(III) complexes: Syntheses, structures, properties and DFT calculations

Four new cyclometalated phenylisoquinoline-based iridium(III) complexes [Ir(C∧N)2(bipy)]PF6 (5a–5d) (bipy=2,2′-bipyridine) have been synthesized and fully characterized, where the C∧N ligands are 1-(4-(trifluoromethyl)phenyl)isoquinoline, 4-(isoquinolin-1-yl)benzaldehyde, 4-(isoquinolin-1-yl)benzonitrile and 1-(3-fluoro-4-methylphenyl)isoquinoline, respectively. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of these new complexes 5a–5d have been studied. All Ir(III) complexes exhibit orange phosphorescence in dichloromethane solution at room temperature with a maximum at 593–618nm, quantum yield of 0.046–0.16. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 5a–5d have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).