Hexa boron-dipyrromethene cyclotriphosphazenes: synthesis, crystal structure, and photophysical properties

We have synthesized four examples of a cyclotriphosphazene ring appended with six boron-dipyrromethene dyes N(3)P(3)(BODIPY)(6) by adopting two different methods. In method I, 1 equiv of N(3)P(3)Cl(6) was treated with 6 equiv of meso-(o- or m- or p-hydroxyphenyl)boron-dipyrromethene in tetrahydrofuran (THF) in the presence of cesium carbonate. This afforded N(3)P(3)(BODIPY)(6) in yields ranging from 80 to 90%. In method II, we first prepared hexakis(p-formylphenoxy)cyclotriphosphazene N(3)P(3)(CHO)(6) by treating 1 equiv of N(3)P(3)Cl(6) with 6 equiv of 4-hydroxybenzaldehyde in the presence of cesium carbonate in THF. In the second step, N(3)P(3)(CHO)(6) was condensed with excess of pyrrole in the presence of catalytic amount of trifluoroacetic acid (TFA) in CH(2)Cl(2) at room temperature and afforded hexakis(p-phenoxy dipyrromethane)cyclotriphosphazene. In the last step, the hexakis(p-phenoxy dipyrromethane)cyclotriphosphazene was first oxidized with 6 equiv of DDQ in CH(2)Cl(2) at room temperature for 1 h followed by neutralization with triethylamine and further reaction with excess BF(3)·Et(2)O afforded the target N(3)P(3)(BODIPY)(6) in 16% yield. The route II was used only for the synthesis of one target compound whereas the route I was used for the synthesis of all four target compounds. The four compounds were characterized by mass, NMR, absorption, electrochemical, and fluorescence techniques. The crystal structure solved for one of the compounds revealed that the P(3)N(3) ring is slightly puckered and the six substituents were not interacting with each other and attained pseudo-axial and pseudo-equatorial positions. The photophysical studies in five different solvents indicated that the compounds exhibit large Stokes' shifts unlike reference monomeric BODIPYs indicating that the compounds are promising for fluorescence bioassays. The quantum yields and lifetimes of compounds 1-4 depends on the type of BODIPY unit attached to the cyclotriphosphazene ring.     

Uranyl oxamate hydrates: hydrothermal synthesis,crystal structure,photophysical properties,and selective crystallization

Presented here are two isostructural uranyl coordination polymers [UO₂(EDO)(H₂O)]·H₂O (1) and [UO₂(BDO)(H₂O)]·2H₂O (2) (EDO^2-=ethylene-1,2-dioxamate; BDO^2-=butylene-1,2-dioxamate) with identical stepwise zigzag chain structure and distinct interchain hydrogen bonding interaction, prepared from hydrothermal reaction of DEEDO or DEBDO (DEEDO=diethyl ethylene-1,2-dioxamate; DEBDO=diethyl butylene-1,2-dioxamate) with uranyl ions. The monomeric uranyl-based fluorescence emissions of compounds 1 and 2 are red-shifted by about 6 and 5 nm respectively, compared to that of uranyl nitrate hexahydrate. Compound 1 has stronger emission than compound 2, but both their emissions exhibit triple-exponential decay. The photophysics of uranyl oxalate trihydrate was also investigated for comparison. The selective crystallization of compound 1 in alkaline solution was applied to the sequestration of uranyl ions, showing a kinetic preference.     

Substituent effect on the photophysical properties, electrochemical properties and electroluminescence performance of orange-emitting iridium complexes

A series of bis(2-phenylbenzothiozolato-N,C(2'))iridium(acetylacetonate) [(bt)(2)Ir(acac)] derivatives, 1-4, were synthesized. Different substituents (CF(3), F, CH(3), OCH(3)) were introduced in the benzothiazole ring to study the substituent effect on the photophysical, electrochemical properties and electroluminescent performance of the complexes, and finally to select high-performance phosphors for use in organic light-emitting diodes (OLEDs). All complexes 1-4 and (bt)(2)Ir(acac) are orange-emitting with tiny spectral difference, despite the variation of the substituent. However, the phosphorescent quantum yield increases with the electron-withdrawing ability of the substituent. This is in contrast to the previous observation that the substituent in the phenyl ring bonded to the metal center of (bt)(2)Ir(acac) not only affected the luminescent quantum efficiency but also greatly tuned the emission color of the complexes. Quantum chemical calculations revealed that the substituents in this position do not make a significant contribution to both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which probably accounts for the fact that they do no strongly influence the bandgap and emission color of the complexes. Orange OLEDs were fabricated using 1-4 as doped emitters. The electron-withdrawing CF(3) and F groups favor improving the electroluminescence efficiency in comparison with that of the parent (bt)(2)Ir(acac), while electron-donating CH(3) and OCH(3) are not favorable for light emission. The complex 1 based OLED exhibited a maximum luminance efficiency of 54.1 cd A(-1) (a power efficiency of 24 lm W(-1) and an external quantum efficiency of 20%), which are among the best results ever reported for vacuum deposited orange OLEDs so far.     

Highly fluorescent pyreno[2,1-b]pyrroles: first syntheses, crystal structure, and intriguing photophysical properties

A series of pyrrole analogues of benzo[a]pyrene have been synthesized in which pyreno[2,1-b]pyrrole exhibits highly fluorescent properties in solution as well as in crystalline form even possessing strong pi-pi stacking. The pi-stacking-induced fluorescence spectral changes lead to future applications such as molecular recognition feasible upon chemical modification.     

Synthesis, crystal structures, and photophysical properties of electron-accepting diethynylindenofluorenediones

A series of 6,12-bis[(trialkylsilyl)ethynyl]indeno[1,2-b]fluorene-5,11-diones has been synthesized. X-ray crystallographic analysis of these compounds reveals that triisopropylsilyl (TIPS) substitution on the alkyne terminus affords the largest number of intermolecular π-π interactions in the solid state. Conversely, use of trialkylsilyl groups smaller or larger than TIPS furnishes a variety of crystal-packing motifs that contain fewer π-π interactions. Electrochemical and photophysical data suggest that these molecules are excellent electron-accepting materials.     

Different crystal structure and photophysical properties of lanthanide complexes with 5-bromonicotinic acid

Five novel lanthanide (Eu³⁺ (1), Tb³⁺ (2), Sm³⁺ (3), Dy³⁺ (4) and Gd³⁺ (5)) complexes with 5-Bromonicotinic acid (5-Brnic) were synthesized and two of them (Tb³⁺, Sm³⁺) were characterized by X-ray diffraction. The results reveal that {[Tb(5-Brnic)₃(H₂O)₃]·H₂O}_n (2) and [Sm(5-Brnic)₃(H₂O)₂·H₂O]₂ (3) exhibit different coordination geometries and crystal structures. Complex 2 has a one-dimensional chain-like polymeric structure through the bridged 5-Brnic anions which links up two neighboring terbium ions, while Complex 3 forms a dimeric molecular structure. The lowest triplet state energy of 5-Brnic was determined to be 24 330 cm⁻¹ corresponded to the 0-0 transition in the phosphorescence spectrum of its gadolinium complex at 411 nm. The strong luminescent emission intensities of these complexes indicated that the triplet state energy of 5-Brnic is suitable for the sensitization of luminescence of Eu³⁺, Tb³⁺, Sm³⁺ and Dy³⁺, especially for that of Tb³⁺ and Dy³⁺.     

A luminescent supermolecule with gold(I) quinoline-8-thiolate: crystal structure,spectroscopic and photophysical properties

The trinuclear complex [(8-QNS)(2)Au(AuPPh(3))(2)].BF(4) (8-QNS = quinoline-8-thiolate), with intramolecular gold(I)...gold(I) distances of 3.0952(4) and 3.0526(3) A, is aggregated to form a novel hexanuclear supermolecule, ([(8-QNS)2(Au(AuPPh3)2])2.(BF4)2, via a close intermolecular gold(I)...gold(I) contact of 3.1135(3) A. The beautiful hexanuclear supermolecule has an inversion center, and the six metal centers can be viewed as roughly coplanar. Six gold(I) ions are embedded in an ellipse and surrounded by 4 quinoline and 12 phenyl rings. The title compound shows interesting spectroscopic and luminescence properties dependent on the solvent polarity; i.e., it emits at ca. 440 and 636 nm in CH(2)Cl(2) and only at ca. 450 nm in CH(3)CN. The long-lived emission at ca. 636 nm (16.2 micros) in CH(2)Cl(2) is quenched by polar solvents such as CH(3)CN and CH(3)OH with quenching constants as 1.00 x 10(5) and 3.03 x 10(4) s(-1) M(-1), respectively, which is suggested to be related to the presence or absence of gold(I)...gold(I) interactions due to scrambling of the [AuPPh(3)]+ units, isolobal to H+.     

Synthesis, crystal structures, and photophysical properties of triphenylamine-based multicyano derivatives

A new series of intramolecular charge transfer (ICT) molecules were synthesized by attaching various strong electron-withdrawing groups to a triphenylamine backbone. Relationships between chemical structures and optoelectronic properties of these compounds were investigated with X-ray diffraction, cyclic voltammetry, absorption spectroscopy, and density functional theory calculations. It is shown that the compounds exhibit intensive ICT interactions leading to substantial extension of their absorption spectral response, which may be potentially used for efficient solar cells.     

Synthesis and photophysical properties of dihydroheptacenes: new blue-emitting materials

7,16-Dihydroheptacenes (1-3) substituted at the 6, 8, 15, and 17 positions are synthesized as blue emitters potentially useful in organic light emitting diodes (OLEDs). The photophysical properties of 1-3 (lambda(max) = 424-428 nm, phi(F) = 0.15-0.21, tau(F) = 2.35-2.67 ns in CH2Cl2) are discussed. They are shown to be stable and efficient blue emitters in the solid state (phi(F) = 0.37-0.44). The X-ray crystal structure of 1 is reported.     

Stable near-infrared anionic polymethine dyes: structure, photophysical, and redox properties

The concept of cyanine has been successfully extended to an anionic heptamethine dye featuring tricyanofuran (TCF) moieties in terms of structure, reactivity, and photophysical properties. Importantly, absorption and emission are red-shifted compared to its classical cationic analog without any cost in terms of thermal stability. In addition to its "cyanine" behavior, this molecule exhibits further redox properties: oxidation and reduction led to the reversible formation of radical species whose absorption is in marked contrast with that of cyanines.     

New cycloplatinated complexes with 2-arylimidazolines: Synthesis, crystal structures and photophysical properties

The synthesis, crystal structures and photophysical properties of a series of cycloplatinated complexes are presented. The complexes have the general formula (C^∧N)Pt(O^∧O), where O^∧O is acetylacetonate and C^∧N represents 2-arylimidazoline ligands. All of them are luminescent in CH₂Cl₂ solution at room temperature. Different aryl group on N-1 of the ligand has no significant effect on the emission properties of the platinum complexes. While introducing alkyl group on N-1 or electron-donating group on 2-aryl ring does result in a blue shift of emission maxima or even an increase in emission intensity.     

Hydroxydialkylamino cruciforms: amphoteric materials with unique photophysical properties

Two amphoteric cruciforms 6 and 7 (XF; 4,4'-[(1E,1'E)-(2,5-bis{[4-(dibutylamino)phenyl]ethynyl}-1,4-phenylene)bis(ethene-2,1-diyl)]diphenol, 4,4'-[{2,5-bis[(E)-4-(dibutylamino)styryl]-1,4-phenylene}bis(ethyne-2,1-diyl)]diphenol) were prepared by a Horner reaction followed by a Sonogashira coupling and subsequent deprotection. The XFs display significant changes in absorption and emission when exposed to trifluoroacetic acid, tetrabutylammonium hydroxide, and metal triflates. The substitution pattern of 6 and 7 leads to spatial separation of the frontier molecular orbitals, which allows the HOMO or LUMO of the XF to be addressed independently by acidic or basic agents. XF 6, which has hydroxyl groups on the styryl axis, displays changes in emission color upon exposure to ten amines in eight different solvents. The change in fluorescence upon the addition of amines was analyzed by linear discriminant analysis. These XFs may have potential in sensor applications for metal cations and amines.     

Theoretical study on photophysical properties of bis-dipolar diphenylamino-endcapped oligoarylfluorenes as light-emitting materials

Bis-dipolar emissive oligoarylfluorenes, OF(2)Ar-NPhs(2), bearing an electron affinitive core, 9,9-dibutylfluorene, as conjugated bridges and diphenylamino as endcaps, show great potential for application in organic light-emitting diodes. The various electron affinitive central aryl cores that include thiophene S,S'-dioxide, dibenzothiophene S,S'-dioxide, 2,1,3-benzothiadiazole, 4,7-dithien-2-yl-2,1,3-benzothiazole, dibenzothiophene, and dibenzofuran produce a remarkable influence on their optical and electronic properties. In this contribution, we apply quantum-chemical techniques to investigate a series of bis-dipolar diphenylamino-endcapped oligoaryfluorenes, OF(2)Ar-NPhs(2). The geometric and electronic structures in the ground state are studied using density functional theory (DFT) and the ab initio HF, whereas the lowest singlet excited states are optimized with ab initio CIS. The maximal absorption and emission wavelengths are investigated by employing time-dependent density functional theory (TDDFT). As a result, HOMOs, LUMOs, energy gaps, ionization potentials, electron affinities, and reorganization energies are affected by varying the electron affinitive cores in OF(2)Ar-NPhs(2). The absorption and emission spectra of this series of bis-dipolar oligoarylfluorenes also exhibit red shifts to some extent due to the electron-withdrawing property and the conjugated length of the electron affinitive cores. Remarkably, their calculated emission spectra can cover the full UV-vis spectrum (from 412 to 732 nm). Also, the Stokes shifes are unexpectedly large, ranging from 34 to 234 nm, resulting from a more planar conformation of the excited state between the two adjacent units in the oligoarylfluorenes. All the calculated results show that the oligoarylfluorenes can be used as hole and electron transport/injection materials in organic light-emitting diodes.     

Cu4I4-cubane cluster based on tris(p-anisyl)arsine: Synthesis,crystal structure and photophysical properties

A new cubane cluster [Cu₄I₄(AsAn₃)₄] was synthesized in 82% yield by the reaction of tris(p-anisyl)arsine (AsAn₃) with CuI. At ambient temperature, this cluster exhibits bright yellow-green phosphorescence (λ_max = 546 nm) with the quantum yield of 35% and 4.1 μs decay time.     

Syntheses,crystal structures,and photophysical properties of two 2-D coordination polymers

Two coordination polymers, [Mn(dipt)(m-BDC)₃] _n (1) and [Pb(mip)(1,4-NDC)] _n (2) [dipt?=?2-(2,4-dichlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, mip?=?2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC?=?isophthalic acid, 1,4-NDC?=?naphthalene-1,4-dicarboxylic acid], have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric analysis, infrared spectrum, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 and 2 have 1-D chain architecture. Complex 1 has a 2-D-layered structure constructed from C–H···O hydrogen bonds. Complex 2 has a 2-D-layered structure constructed from N–H···O hydrogen bonds and π–π interactions. TG analyses suggest 1 and 2 have excellent thermal stabilities from hydrogen bonds and π–π interactions. Mn(II) in 1 has trigonal bipyramidal geometry surrounded by three carboxylate oxygen atoms from three monodentate bridging m-BDC and two nitrogen atoms from one dipt. Pb(II) has [:PbN2O4] pentagonal bipyramidal geometry in 2. The luminescent properties for dipt, mip, 1, and 2 are also presented.     

Fluorenyl hexa-peri-hexabenzocoronene-dendritic oligothiophene hybrid materials: synthesis, photophysical properties, self-association behaviour and device performance

Apart from molecular properties, intermolecular forces play a vital role in defining the performance of organic electronic devices. This is particularly relevant in bulk heterojunction (BHJ) solar cells in which the arrangement of electron-donor and -acceptor materials into distinct crystalline phases of ideal size and distribution can lead to better power conversion efficiencies. In this study, a series of fluorenyl hexa-peri-hexabenzocoronenes (FHBC) decorated with thiophene dendrons (DOT) of variable size was obtained by using a convergent synthetic approach. With such variety of molecular sizes and shapes in hand, the objective of this study is to highlight the relationships between molecular properties, bulk properties and device performance. Correlations between π-π stacking ability and dendrimer generation were established from self-organisation studies in solution and solid state. The synergistic combination of molecular organisation at the nanoscale and photophysical characteristics derived from the FHBC and DOT moieties leads to a notable improvement of the photovoltaic performance.     

Synthesis, crystal structures, and photophysical properties of homodinuclear lanthanide xanthene-9-carboxylates

Three new homodinuclear lanthanide(III) complexes of xanthene-9-carboxylic acid, [Ln2(XA)6(DMSO)2(H2O)2](Ln = Eu (1), Tb (2) and Gd (3); HXA = xanthene-9-carboxylic acid; DMSO = dimethylsulfoxide), have been synthesized, of which 1 and 2 were structurally characterized by single-crystal X-ray diffraction. These compounds crystallize in the monoclinic space group P21/n with a =17.849(4) A, b = 9.6537(19) A, c = 23.127(5) A, beta = 109.06(3) degrees , and V = 3766.5(13) A3 for 1 and a =17.809(4) A, b = 9.6548(19) A, c = 23.075(5) A, beta = 108.97(3) degrees , and V = 3752.1(13) A3 for 2. The crystal structures of 1 and 2 consist of homodinuclear species that are bridged by two oxygen atoms from two carboxylate ligands. The two lanthanide ions are related by a center of inversion. Each lanthanide ion is coordinated by eight oxygen atoms in an overall distorted square-prismatic geometry. Six of the oxygen atoms are furnished by the carboxylate moieties, and the remaining two oxygen atoms are provided by water and DMSO molecules. The photophysical properties of these complexes in the solid state at room temperature have been investigated. The quantum yields were found to be 0.06 +/- 0.01 and 7.30 +/- 0.73% for 1 and 2, respectively.     

Mononuclear and dinuclear complexes of dibenzoeilatin: synthesis, structure, and electrochemical and photophysical properties

This work describes a study of Ru(II) and Os(II) polypyridyl complexes of the symmetrical, fused-aromatic bridging ligand dibenzoeilatin (1). The synthesis, purification, and structural characterization by NMR of the mononuclear complexes [Ru(bpy)(2)(dbneil)](2+) (2), [Ru(tmbpy)(2)(dbneil)](2+) (3), and [Os(bpy)(2)(dbneil)](2+) (4), the homodinuclear complexes [[Ru(bpy)(2)](2)[micro-dbneil]](4+) (5), [[Ru(tmbpy)(2)](2)[micro-dbneil]](4+) (6), and [[Os(bpy)(2)](2)[micro-dbneil]](4+) (7), and the heterodinuclear complex [[Ru(bpy)(2)][micro-dbneil][Os(bpy)(2)]](4+) (8) are described, along with the crystal structures of 4, 6, and 7. Absorption spectra of the mononuclear complexes feature a low-lying MLCT band around 600 nm. The coordination of a second metal fragment results in a dramatic red shift of the MLCT band to beyond 700 nm. Cyclic and square wave voltammograms of the mononuclear complexes exhibit one reversible metal-based oxidation, as well as several ligand-based reduction waves. The first two reductions, attributed to reduction of the dibenzoeilatin ligand, are substantially anodically shifted compared to [M(bpy)(3)](2+) (M = Ru, Os), consistent with the low-lying pi orbital of dibenzoeilatin. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the conjugated dibenzoeilatin ligand. Luminescence spectra, quantum yield, and lifetime measurements at room temperature in argon-purged acetonitrile have shown that the complexes exhibit (3)MLCT emission, which occurs in the IR-region between 950 and 1300 nm. The heterodinuclear complex 8 exhibits luminescence only from the Ru-based fragment, the intensity of which is less than 1% of that observed in the corresponding homodinuclear complex 5; no emission from the Os-based unit is observed, and an intramolecular quenching constant of k(q) > or = 3 x10(9) s(-)(1) is evaluated. The nature of the quenching process is briefly discussed.     

Well-defined enantiopure 1,1'-binaphthyl-based oligomers: synthesis,structure, photophysical properties,and chiral sensing

A series of well-defined enantiopure 1,1'-binaphthyl-based oligomers linked through their 6,6'-positions, ranging from quaternaphthol to decanaphthol, have been synthesized by Suzuki and Stille coupling reactions. These novel oligonaphthyls have been characterized by (1)H and (13)C[(1)H] NMR spectroscopy and high-resolution mass spectrometry. A combination of X-ray structural and CD studies suggests that these oligonaphthyls adopt zigzag but not helical conformations. As the chain length increases, the compounds show enhanced fluorescence. The fluorescence intensity of oligonaphthols is almost 2 orders of magnitude higher than that of 1,1'-bi-2-naphthol and can be effectively and enantioselectively quenched with trans-1,2-diaminocyclohexane with an enantioselectivity factor of 1.24. The present work thus demonstrates the potential of constructing chiral sensory materials based on well-defined enantiopure oligonaphthols.