Structureless Emission Research Articles

Synthesis, structures and properties of new cyclometalated iridium(III) complexes of 3-methoxy-6-methyl-2-(naphthalen-2-yl)pyridine

The reaction between 3-methoxy-6-methyl-2-(naphthalen-2-yl)pyridine 1 and IrCl 3 was performed in an attempt to synthesize a cyclometalated Ir(III) Cl-bridged dimer 2. An unexpected Ir(III) complex 3 was isolated, which was a five-coordinate bis-cyclometalated Ir(III) complex. The complexes 2 and 3 were converted to the same mononuclear complex 4 upon reacting with acetylacetonate (acac), respectively. All of the new compounds have been fully characterized by elemental analysis, IR, 1H, 13C{ 1H} NMR and ESI-MS. Additionally, the crystal structures and properties of these Ir(III) complexes are investigated. The most striking common features of the structures of 2 and 3 is intramolecular C–H···Cl hydrogen bonds. The complex 4 shows yellow phosphorescence with structureless emission peaks at about 556 nm.

Installation/Modulation of the Emission Response via Click Reaction

We have demonstrated the installation of a fluorescence property into a nonfluorescent precursor and modulation of an emission response of a pyrene fluorophore via click reaction. The synthesized fluorophores show different solvatochromicity and/or intramolecular charge transfer (ICT) feature as is revealed from the UV-visible, fluorescence photophysical properties of these fluorophores, and DFT/TDDFT calculation. We observed that some of the synthesized fluorophores showed purely ICT character while emission from some of them arose from the LE state. A structureless and solvent polarity-sensitive dual emission behavior was observed for one of the triazolylpyrene fluorophores that contains an electron-donating -NMe(2) substituent (fluorophore, 7a). Conversely, triazolylpyrene with an electron-withdrawing -CN group (fluorophore, 7b) showed a solvent polarity-independent vibronic emission. The effect of ICT on the photophysical properties of these fluorophores was studied by fluorescence emission spectra and DFT/TDDFT calculations. Fluorescence lifetimes were also measured in different solvents. All of our findings revealed the delicate interplay of structure and emission properties and thus having broader general utility. As the CT to LE intensity ratio can be employed as a sensing index, the dual emissive fluorophore can be utilized in designing the molecular recognition system too. We envisage that our investigation is of importance for the development of new fluorophores with predetermined photophysical properties that may find a wide range of applications in chemistry, biology, and material sciences.

Determinants of the structured and structureless green emissions of ZnO

Green emission can be identified as either a structured or a structureless emission. In the downward surface band bending region, the influence of defects on the continuous change in the 0–0 electronic transition was found to be a dominating factor that differentiates the characteristics of green emission. Such a change in the 0–0 electronic transition gives rise to the structureless green emission at higher energy, while the 0–0 electronic transition in the bulk of ZnO plays an important role resulting in structured green emission with lower energy.

Ultrafast Intramolecular Charge Transfer with N-(4-Cyanophenyl)carbazole. Evidence for a LE Precursor and Dual LE + ICT Fluorescence

The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE → ICT reaction time τ(2) at 22 °C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the ICT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE ⇄ ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S(0) → S(n) absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of ∼4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 °C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE → ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE fluorescence. For the series of D/A molecules NPC, N-(4-fluorophenyl)carbazole (NP4F), N-[4-(trifluoromethyl)phenyl]carbazole (NP4CF), and NP4CN, with increasing electron affinity of their phenyl subgroup, an ICT emission in n-hexane 25 °C only is present for NP4CN, whereas in MeCN an ICT fluorescence is observed with NP4CF and NP4CN. The ICT fluorescence appears when for the energies E(ICT) of the ICT state and E(S(1)) of the lowest excited singlet state the condition E(ICT) ≤ E(S(1)) holds. E(ICT) is calculated from the difference E(D/D(+)) - E(A(-)/A) of the redox potentials of the D and A subgroups of the N-phenylcarbazoles. From solvatochromic measurements with NP4CN an ICT dipole moment μ(e)(ICT) = 19 D is obtained, somewhat larger than the literature values of 10-16 D, because of a different Onsager radius ρ. The carbazole/phenyl twist angle θ = 45° of NP4CN in the S(0) ground state, determined from X-ray crystal analysis, has become smaller for its ICT state, in analogy with similar conclusions for related N-phenylcarbazoles and other D/A molecules in the literature.

Luminescent Cyclometalated Dialkynylgold(III) Complexes of 2‐Phenylpyridine‐Type Derivatives with Readily Tunable Emission Properties

A novel class of luminescent dialkynylgold(III) complexes containing various phenylpyridine and phenylisoquinoline-type bidentate ligands has been successfully synthesized and characterized. The structures of some of them have also been determined by X-ray crystallography. Electrochemical studies demonstrate the presence of a ligand-centered reduction originating from the cyclometalating C^N ligand, whereas the first oxidation wave is associated with an alkynyl ligand-centered oxidation. The electronic absorption and photoluminescence properties of the complexes have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the metal-perturbed π-π* intraligand (IL) transition of the cyclometalating C^N ligand, with mixing of charge-transfer character from the aryl ring to the pyridine or isoquinoline moieties of the cyclometalating C^N ligand. The low-energy emission bands of the complexes in fluid solution at room temperature are ascribed to originate from the metal-perturbed π-π* IL transition of the cyclometalatng C^N ligand. For complex 4 that contains an electron-rich amino substituent on the alkynyl ligand, a structureless emission band, instead of one with vibronic structures as in the other complexes, was observed, which was assigned as being derived from an excited state of a [π(C≡CC(6) H(4) NH(2) )→π*(C^N)] ligand-to-ligand charge-transfer (LLCT) transition.

Red‐NIR Luminescent Hybrid Poly(methyl methacrylate) Containing Covalently Linked Octahedral Rhenium Metallic Clusters

The embedding of functional inorganic entities into polymer matrices has become an intense field of investigation in which the main challenges are to keep the added value of the inorganic entities while preventing their self-aggregation within the organic matrix. We present a simple way to obtain a homogeneous highly red-NIR luminescent hybrid copolymer that contains covalently bonded nanometric-sized {Re(6)} octahedral clusters. The [Re(6)Se(i)(8)(OH)(a)(6)](4-) cluster complexes are primarily functionalized in two steps with tert-butylpyridine (TBP) and methacrylic acid (MAC) to give neutral [Re(6)Se(8)(TBP)(4)(MAC)(2)] building blocks that are copolymerized with methyl methacrylate (MMA) either in solution or in bulk in the presence of azobisisobutyronitrile as an initiator. Several samples containing 0, 0.025, 0.05, and 0.1 wt % of functionalized {Re(6)} clusters were prepared. As the {Re(6)} cluster/MMA ratio is very low, the obtained copolymers keep the entire processability of pure poly(methyl methacrylate) (PMMA), as demonstrated by differential scanning calorimetry and thermogravimetric analysis. Voltammetric and luminescence studies also indicate that the intrinsic properties of the clusters are preserved within the polymer matrix. All the samples show a bright (emission quantum yield=0.07), broad, and structureless emission band, which extends from lambda=600 nm to more than lambda=950 nm, with the maximum wavelength centered around lambda(em)=710 nm either in solution or in the solid state. Moreover, the high stability of the incorporated inorganic phosphors prevents the material from photobleaching, and thus the luminescence properties are kept entirely even after nine months of ageing.

Thermochromism of a Poly(phenylene vinylene): Untangling the Roles of Polymer Aggregate and Chain Conformation

We report reversible thermochromism of a conjugated polymer, poly{2,5-bis[3-(N,N-diethylamino)-1-oxapropyl]-1,4-phenylenevinylene} (DAO-PPV), in diluted solutions of toluene and 1,2-dichlorobenzene. By means of temperature- and solvent-dependent steady-state spectroscopy, picosecond time-resolved photoluminescence spectroscopy, and dynamic light scattering, we provide new insights into the role of polymer aggregates in defining the thermochromic behavior of PPVs. We find DAO-PPV to exhibit a low temperature state with vibronically structured red visible absorption and emission spectra. Structurally, this low temperature state is a densely packed and disordered polymer aggregate, which contains a fraction of well-ordered, packed polymer chains. These ordered regions serve as low energy trap sites for the more disordered regions in the aggregate, thus regulating the final emission of the aggregate and imposing a vibronically resolved emission spectrum, which is usually associated with emission from one or a few chromophores. The high temperature state of DAO-PPV is a loose aggregate, with structureless absorption and emission spectra in the green visible range. Structurally, the loose aggregate is a well-solvated aggregate retaining the physical dimension of the dense aggregate but for which interchain interactions are diminished with the increase of temperature. As a result, the spectroscopic behavior of the loose aggregate is very similar if not identical to that of the single polymer chain. Increased solubility untangles polymer aggregates into single, dispersed, polymer chains, as we demonstrate here for DAO-PPV in 1,2-dichlorobenzene and at high temperature.

Photophysics in Platinum(II) Bipyridylacetylides

The synthesis, structural characterization, photoluminescence, and excited state absorption properties of a series of platinum(II) terpyridyl complexes bearing a bipyridyl acetylide subunit are presented. The [(t)Bu(3)tpyPtC identical withCbpy](+) (1) complex displays a broad and structureless emission profile at room temperature (RT), a lifetime of 5.8 mus, and transient absorption (TA) difference spectra characteristic of a charge transfer (CT) excited state. Upon coordination of Fe(2+) to 1, producing tetranuclear 2, the CT emission was quantitatively quenched presumably through the low-lying iron-based ligand field states present. Surprisingly, the addition of Zn(2+) to solutions of 1 produces a higher energy emissive state with a substantially longer excited state lifetime of 16.1 mus. The combined spectroscopic data measured for the zinc titration product (3) suggests that the overall excited state is dominated by a CT manifold, albeit at higher energy relative to 1. The photophysics of a bis-phosphine complex bearing two trans-disposed bpy-acetylide subunits (4) produced a model chromophore possessing an intraligand triplet excited state with a lifetime of 26 mus at RT. The bipyridyl analogue of 1, (t)Bu(2)bpyPt(C identical withCbpy)(2) (5), was also prepared and its photophysics are consistent with a lowest CT parentage at RT. The 77 K emission spectra measured for complexes 1, 3, 4, and 5 are all consistent with a triplet bpy-acetylide localized excited state; the E(00) energies vary over a modest 344 cm(-1) across the series. However, the shorter 77 K excited state lifetimes observed for 1, 3, and 5 in comparison to 4 suggests that the energetically proximate CT state in the former compounds significantly influences excited state decay at low temperature.

Shape-Persistent Oligothienylene-Ethynylene-Based Dendrimers: Synthesis, Spectroscopy and Electrochemical Characterization

A series of novel structurally well-defined oligothienylene-ethynylene-based dendritic macromolecules up to the 3rd generation (G3) were successfully synthesized by a combination of Pd-catalyzed Sonogashira-type cross-coupling and oxidative homocoupling steps. Oxidative homocoupling of dendrons successfully afforded dendrimers up to the 2nd generation (G2). In contrast, the G3 dendrimer was effectively prepared by a four-fold Sonogashira-type cross-coupling reaction. All compounds showed broad and structureless absorption and emission spectra arising from the presence of different pi-conjugated chromophores. With increasing generation, a bathochromic shift of the pi-pi* absorption band and an increase of the absorption coefficient were observed. The insertion of ethynylene groups into the conjugated dendrimer backbone resulted in a hypsochromic shift compared to all-thiophene dendrimers reported earlier by our group. All dendritic compounds are fluorescent and showed moderate quantum efficiencies due to an effective intramolecular charge-transfer (ICT) process. Cyclic voltammetry measurements also revealed the presence of multiple pi-conjugative pathways that show very broad oxidation waves for higher generations. HOMO-LUMO energy levels of these dendrons and dendrimers were estimated from optical and redox measurements and the calculated band gaps were within the range of 3.3 to 2.4 eV, typical for oligo- and polythiophenes. Electrochemical polymerizations of several desilylated compounds were performed and characterization of the films is reported. Preliminary bulk heterojunction solar cells that utilise these ethynylated dendrimers as the donor and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM[60]) as the acceptor showed moderate efficiencies ranging from 0.18-0.64%.

Self-trapped excitonic green emission from layered semiconductors

Crystals of layered semiconductor are grown by Bridgman technique and are studied them under two-photon excitation by a Q-switched 20-ns pulse laser. The photoluminescence (PL) emission spectra of the crystals are measured at various pumping powers and temperatures. The PL spectra appear broad and structureless emissions with their peaks in the green spectral region. The characteristic emissions are from self-trapped excitons of the crystals. An analysis of the spectra measured at various pumping powers shows a quadratic dependence of the PL peak intensity on the power, confirming a biphotonic process of the two-photon pumping. The temperature dependence shows an enhancement of the nonlinear response at low temperatures. The activation energy is estimated and found to be 2.4 meV. The roles of the bound excitons in the observed PL are discussed briefly.

Synthesis, Thermal, and Light-Emitting Properties of Anthracene Derivatives

Several anthracene derivatives were prepared by a single-step reaction and characterized their thermal properties by differential scanning calorimetry (DSC) and thermogravimetric analyses. Their photoluminescence properties were examined in a large number of organic solvents of increased polarity that included toluene, chloroform, tetrahydrofuran, acetone, methanol, acetonitrile, and dimethyl sulfoxide. Some compounds exhibited emission spectra with vibrational fine structures in organic solvents; and other compounds exhibited structureless emission spectra in organic solvents.

Sulfur dioxide measurements using an ultraviolet light-emitting diode in combination with gas correlation techniques

The important air pollutant sulfur dioxide has a strong structured absorption band in the ultraviolet (UV) region around 300 nm. Recently, light-emitting diodes (LEDs) with structureless emission in a band about 15-nm wide in the UV region have become available. We demonstrate that they can be ideal sources for gas absorption measurements combined with the gas correlation technique, where an absorption cell with an optically thick column of the gas under investigation is used for analysing the target gas contents in a path between the LED and the measurement device. A sensitivity of 0.4 ppm sulfur dioxide was obtained with a 19-cm optical path length and 60-s integration time. Particularly compact and cost-effective monitors especially for industrial emissions can be envisaged.

New Water Soluble and Luminescent Platinum(II) Compounds, Vapochromic Behavior of [K(H2O)][Pt(bzq)(CN)2], New Examples of the Influence of the Counterion on the Photophysical Properties of d8 Square-Planar Complexes

This work describes the synthesis of compounds [Pt(C=N)(NCMe) 2]ClO 4 (C=N = 7,8-benzoquinolinato (bzq), 2-phenylpyridinato (ppy)) and their use as precursors for the preparation of the cyanido complexes [Pt(C=N)(CN) 2] (-), which were isolated as the potassium, [K(H 2O)][Pt(C=N)(CN) 2] [C=N = bzq ( 3a), ppy ( 4a)], and the tetrabutylammonium, NBu 4[Pt(C=N)(CN) 2] [C=N = bzq ( 5), ppy ( 6)], salts. The difference in the cation has an influence on the solubility, color, and emission properties of these compounds. Compounds 5 and 6 are yellow and soluble in organic solvents, while the potassium salts are also soluble in water and exhibit two forms: the water-containing [K(H 2O)][Pt(C=N)(CN) 2] [C=N = bzq ( 3a), ppy ( 4a)] complexes and the anhydrous ones K[Pt(C=N)(CN) 2] [C=N = bzq ( 3b), ppy ( 4b)], the former being strongly colored [red ( 3a) or purple ( 4a)] and the latter being yellow. Compounds 3a and 4a transform reversibly into the yellow, 3b and 4b, compounds upon desorption/ reabsorption of water molecules from the environment. The red solid, 3a, also exhibits vapochromic behavior when it is exposed to volatile organic compounds, the shortest response times being those observed for methanol and ethanol. UV-vis and emission spectra of all compounds were recorded both in solution and in the solid state. In methanol solution, the difference in the cation causes no differences in the absorption nor in the emission spectra, which is as expected for the monomer species. However, in the solid state, the differences are notable. For both the red ( 3a) and purple ( 4a) compounds, a prominent absorption, which has maxima at about 550 nm and is responsible for their intense colors, as well as a structureless emission at lambda > 700 nm that suffers a significant red-shift upon cooling, are due to (1,3)MMLCT (= metal-metal-to-ligand charge transfer) [dsigma*(Pt) --> pi*(C=N)] transitions characteristic of linear-chain platinum complexes with short Pt...Pt contacts. Time-dependent density-functional theory calculations on complex 5 and the X-ray diffraction study on compound [K(OCMe 2) 2][Pt(ppy)(CN) 2] ( 4c) are also included.

Photophysics of the Platinum(II) Terpyridyl Terpyridylacetylide Platform and the Influence of FeIIand ZnIICoordination

The synthesis, structural characterization, and photoluminescence (PL) properties of the square-planar terpyridylplatinum(II) complex [ ( t )Bu 3tpyPtCCtpy] (+) ( 1) and the octahedral trinuclear Fe (II) and Zn (II) analogues [Fe( ( t )Bu 3tpyPtCCtpy) 2] (4+) ( 2) and [Zn( ( t )Bu 3tpyPtCCtpy) 2] (4+) ( 3) are described. The photophysical properties of the mononuclear Pt (II) complex 1 are consistent with a charge-transfer excited-state parentage producing a large Stokes shift with a concomitant broad, structureless emission profile. The Fe-based ligand-field states in 2 provide an efficient nonradiative deactivation pathway for excited-state decay, resulting in a nonemissive compound at room temperature. Interestingly, upon chelation of 1 with Zn (II), a higher energy charge-transfer emission with a low-energy shoulder and a 215 ns excited-state lifetime is produced in 3. A spectroscopically identical species relative to 3 was produced in control experiments when 1 was reacted with excess protons (HClO 4) as ascertained by UV-vis and static PL spectra measured at room temperature and 77 K. Therefore, the chelation of Zn (II) to 1 is acid-base in nature, and its Lewis acidity renders the highest occupied molecular orbital level in 1 much less electron-rich, which induces a blue shift in both the absorption and emission spectra. At 77 K, complexes 1, 3, and protonated 1 display at least one prevalent vibronic component in the emission profile (1360 cm (-1)) resembling PL emanating from a ligand-localized excited-state, indicating that these emitting states are inverted relative to room temperature. These results are qualitatively confirmed by the application of time-dependent theory using only the 1360 cm (-1) mode to reproduce the low-temperature emission spectra.

Luminescent Alkynylplatinum(II) Complexes of 2,6‐Bis(N‐alkylbenzimidazol‐2′‐yl)pyridine‐Type Ligands with Ready Tunability of the Nature of the Emissive States by Solvent and Electronic Property Modulation

A new class of luminescent alkynylplatinum(II) complexes of tridentate bis(N-alkylbenzimidazol-2'-yl)pyridines (bzimpy), [Pt(R,R'-bzimpy)(C[triple chemical bond]C-R'')]X (X=PF(6), OTf), and one of their chloro precursor complexes, [Pt(R,R'-bzimpy)Cl]PF(6), have been synthesized and characterized; one of the alkynyl complexes has also been structurally characterized by X-ray crystallography. Electrochemical studies showed that the oxidation wave is alkynyl ligand-based in nature with some mixing of the metal center-based contribution, whereas the two quasi-reversible reduction couples are mainly bzimpy-based reductions. The electronic absorption and luminescence properties of the complexes have also been investigated. In solution, the high-energy and intense absorption bands are assigned as the pi-pi* intraligand (IL) transitions of the bzimpy and alkynyl ligands, whereas the low-energy and moderately intense absorptions are assigned to an admixture of metal-to-ligand charge-transfer (MLCT) (dpi(Pt)-->pi*(R,R'-bzimpy)) and ligand-to-ligand charge-transfer (LLCT) (pi(C[triple chemical bond]C-R'')-->pi*(R,R'-bzimpy)) transitions. Upon variation of the electronic effects of the arylalkynyl ligands, vibronic-structured or structureless emission bands, originating from triplet metal-perturbed intraligand (IL) or an admixture of triplet metal-to-ligand charge-transfer (MLCT) and ligand-to-ligand charge-transfer (LLCT) excited states respectively, were observed in solution. Interestingly, two of the complexes showed a dual luminescence that was sensitive to the polarity of the solvents. Upon cooling from 298 K to 155 K, drastic color, UV/Vis, and luminescence changes were observed in a butyronitrile solution of 1, and were ascribed to the formation of aggregate species through PtPt and pi-pi stacking interactions. DFT and time-dependent DFT (TD-DFT) calculations have been performed to verify and elucidate the results of the electrochemical and photophysical properties.

Intramolecular exciplexes based on benzoxazole: photophysics and applications as fluorescent cation sensors

Exciplex behaviour of three benzoxazole derivatives has been detected and intensively investigated by means of steady-state and time-resolved fluorescence techniques and transient absorption spectroscopy. The fluorescence of these compounds shows the properties which are typical for the excited state charge transfer complexes (exciplexes). Besides of the short wavelength fluorescence, which is similar in spectral distribution to the fluorescence of the electron acceptor (2-p-tolyl-benzoxazole), the red shifted, broad and structureless emission band is observed in solvents of low and medium polarity. The detailed analysis of the fluorescence data shows that the ratio of the CT and LE fluorescence initially increases with increasing solvent polarity, achieves a maximum, and drops for more polar solvents (epsilon(s) = 7). Similar behaviour is observed for the exciplex fluorescence lifetimes. The overall fluorescence and the relative intersystem crossing quantum yields show the decrease of these values with increasing solvent polarity. These observations have been explained on the basis of Marcus-type theory for nonradiative charge transfer rate constants. Increasing solvent polarity strongly accelerates the back electron transfer process which recovers the whole molecule in the ground state. The probability of the compact exciplex formation (i.e. sandwich-type structures) depends on solvent viscosity and degree of freedom of the bending of the saturated linker. The compound containing crown ether as a donor subunit may be used as a fluorescent indicator of inorganic cations (barium and lithium). We found an effective complexation of the compound in the ground state with barium and lithium cations. The complex is also stable in the excited state which manifests itself in strong increase of the fluorescence intensity.

New contributions to the photophysical model for all-trans-polyenesfrom ttbP4, a nonphotolabile octatetraene

All-trans-octatetraene 3,10-di(tert-butyl)-2,2,11,11-tetramethyl-3,5,7,9-dodecatetraene emits fluorescence in three different regions of the visible spectrum. Thus, it produces an extremely weak emission in the gas phase that can hardly be detected in the condensed phase; such an emission exhibits a negligible Stokes shift with respect to the 1A(g)-->1B(u) absorption transition and can, in principle, be assigned to the 1B(u)-->1A(g) emission for the compound. A second, structureless fluorescence emission, centered in the region of 525 nm, is observed in the gas phase and at somewhat higher wavelengths in the condensed phase [viz., 570 nm in 2-methylbutane (2MB) and 550 nm in squalane (SQ)]. While detectable, this emission increases significantly, with no change in spectral position, as the solution temperature is lowered; also, it is abruptly replaced by a new, strongly blueshifted emission at approximately 490 nm in 2MB and 455 mm in SQ when the viscosity of the medium exceeds a given level. The fact that the two fluorescence emissions considerably depart from the expected behavior for a 1B(u)-->1A(g) emission in an all-trans-polyene, and that one disappears while the other simultaneously appears as the medium becomes more rigid, suggests that the two emissions are produced by two different molecular structures and that the rigidity of the medium switches their production from the originally excited all-trans 1B(u) form. The observed spectral behavior is consistent with a recently proposed model [J. Catalan, Chem. Phys. 335, 69 (2007)] in which the 1B(u) excited state of octatetraene can give two distinct molecular conformers as a result of twisting about different C-C single bonds.

Photoinduced Electron Transfer in Coaggregates of Dicyanonaphthalene and Pyrazoline

The photophysical properties of mixed coaggregates containing 1,4-dicyanonaphthalene (DCN) and 1,3,5-triphenyl-2-pyrazoline (TPP) have been studied. The absorption spectra of mixed coaggregates indicate that a charge-transfer complex is not formed in the ground state between DCN and TPP. The fluorescence of TPP in the mixed coaggregates is quenched by DCN, accompanied with a broad and structureless emission at about 560 nm from an exciplex between DCN and TPP. The color of the emission from mixed coaggregates is tunable by changing the DCN content. The excited-state properties of the TPP-DCN molecule pair are investigated theoretically with a quantum chemistry method. The theoretical results have also confirmed that the broad emission at about 560 nm in the mixed coaggregates originates from the exciplex rather than from the charge-transfer complex.

Fluorinated Diphenylpolyenes: Crystal Structures and Emission Properties

(E,E,E)-1,6-Diaryl(Ar)-1,3,5-hexatrienes (2, Ar = 4-fluorophenyl; 3, Ar = 2,4-difluorophenyl; 4, Ar = 2,4,6-trifluorophenyl; 5, Ar = perfluorophenyl) and (E,E,E)-1-perfluorophenyl-6-phenyl-1,3,5-hexatriene (6) were prepared. The absorption and fluorescence spectra in methylcyclohexane solution showed only a small dependence on the fluorine ring substituent, and were similar to those of the unsubstituted parent compound (1, Ar = phenyl). The solid-state absorption and fluorescence spectra shifted to red relative to those in solution and strongly depended on the substituent. The emission from crystals 1-5 originated mainly from monomeric species with the maximum wavelength (lambda f(max)) of 440-465 nm, which overlapped the emission from molecular aggregates (1-4) or excimeric species (5) in the red region. Crystal 6 exhibited red-shifted (lambda f(max) = 530 nm) and structureless emission due to excimers. The cocrystal of 1 and 5 (1/5) showed red-shifted (lambda f(max) = 558 nm) and distinctly structured emission, not from exciplexes but from the excited states of molecular aggregates in which molecules 1 and 5 strongly interact already in the ground state. These assignments were confirmed by the results of fluorescence lifetime and quantum yield measurements in the solid state. Single-crystal X-ray structure analyses showed that the molecules were basically planar in each crystal, whereas the crystal packing was strongly substituent-dependent. Weak pi-pi interactions in the herringbone (1 and 2) and in the pi-stacked but largely offset structures (3 and 4) account for their predominantly monomeric origin of emission. The observation of excimer fluorescence from 5 was rather unexpected, since the molecules in this crystal were arranged in an offset stacking fashion due to perfluorophenyl-perfluorophenyl (C6F5...C6F5) interaction. The structures of 6 and 1/5 considerably resembled each other, in which molecules were pi-stacked with more face-to-face geometries than those in 5, as a result of strongly attractive perfluorophenyl-phenyl (C6F5...C6H5) interaction. Nevertheless, the fluorescence origin was clearly different for 6 and 1/5. This can be ascribed to the difference in the strength of orbital-orbital interaction between molecular pi-planes in the ground and excited states in crystals.

Cis-Dicyanoosmium(II) Diimine Complexes Bearing Phosphine or Sulfoxide Ligands: Spectroscopic and Luminescent Studies

A series of cis-dicyanoosmium(II) complexes [Os(PPh3)2(CN)2(N intersectionN)] (N intersectionN = Ph2phen (2a), bpy (2b), phen (2c), Ph2bpy (2d), tBu2bpy (2e)) and [Os(DMSO)2(CN)2(N intersectionN)] (3a-3e, N intersectionN = Br2phen (3f), Clphen (3g)), were synthesized and their spectroscopic and photophysical properties were examined, and [Os(PMe3)2(CN)2(phen)] (4) with axial PMe3 ligands was similarly prepared. The molecular structures of 2a, 2c, [2c.Zn(NO3)2]infinity, 2d, 2e, 3b, 3d, 3e, and 4 were determined by X-ray crystallographic analyses. The two CN ligands are cis to each other with mean Os-C bond distance of 2.0 A. The two PR3 (R = Ph, Me) or DMSO ligands are trans to each other with P/S-Os-P/S angles of approximately 177 degrees . The UV-vis absorption spectra of 2a-2e display an intense absorption band at 268-315 nm (epsilon = approximately (1.54-4.82) x 104 M-1 cm-1) that are attributed to pi --> pi*(N intersection N) and/or pi --> pi*(PPh3) transitions. The moderately intense absorption bands with lambdamax at 387-460 nm (epsilon = approximately (2.4-11.3) x 103 M(-1) cm(-1)) are attributed to a 1MLCT transition. A weak, broad absorption at 487-600 nm (epsilon = approximately 390-1900 M(-1) cm(-1)) is assigned to a 3MLCT transition. Excitation of 2a-2e in dichloromethane at 420 nm gives an emission with peak maximum at 654-703 nm and lifetime of 0.16-0.67 micros. The emission energies, lifetimes, and quantum yields show solvatochromic responses, and plots of numax, tau, and Phi, respectively, versus ET (solvent polarity parameter) show linear correlations, indicating that the emission is sensitive to the local environment. The broad structureless solid-state emission of 2a-2e at 298 (lambdamax 622-707 nm) and 77 (lambdamax 602-675 nm) K are assigned to 3MLCT excited states. The 77 K MeOH/EtOH (1:4) glassy solutions of 2a-2e also exhibit 3MLCT emissions with lambdamax = 560-585 nm. The 1MLCT absorption and 3MLCT emission of 3a-3g occur at lambdamax = 332-390 nm and 553-644 nm, respectively. In the presence of Zn(NO3)2, both the 1MLCT absorption and 3MLCT emission of 2c in acetonitrile blue-shift from 397 to 341 nm and 651 to 531 nm, respectively. The enhancement of emission intensity (I/Io) of 2e at 531 nm reached a maximum of approximately 810 upon the addition of two equivs of Zn(NO3)2. The crystallographic and spectroscopic evidence suggests that 2c undergoes binding of Zn2+ ions via the cyano moieties.