CT Character Research Articles

Two luminescent pseudo-polymorphic cuprous complexes with different optical properties: Synthesis, characterization and TD-DFT calculations

Two luminescent pseudo-polymorphs based on a new cuprous complex, [Cu(2-iQBO)(POP)]PF6 (2-iQBO = 2-(1′-isoquinolyl)benzoxazole, POP = bis[2-(diphenylphosphino)phenyl]ether), have been synthesized and characterized by UV–Vis, elemental analysis and single-crystal X-ray diffraction analyses. The pseudo-polymorphs 1 and 2 are characterized as a dichloromethane solvate and an acetonitrile solvate, respectively. Single-crystal X-ray diffraction data reveal that 1 and 2 are both mononuclear cuprous complexes with a tetrahedral CuN2P2 coordination configuration, consisting of two P atoms from the POP ligand and two N atoms from the 2-iQBO ligand. The pseudo-polymorphic complexes 1 and 2 can be distinguished by their crystal color, UV–Vis spectra and PL spectra. Time-dependent density functional theory (TD-DFT) calculations reveal that the P–Cu–P angle is a key structural factor influencing the absorption and emission properties. Based on the TD-DFT calculations, the lowest singlet excited state corresponding to the UV–Vis absorption edge can be definitely assigned as a metal-to-ligand charge transfer (MLCT) mixed with a ligand-to-ligand charge transfer (L'LCT), and the lowest triplet excited states should be both assigned as a mixed 3(ML + L'L)CT character.

How are the charge transfer descriptors affected by the quality of the underpinning electronic density?

With the aim of investigating qualitatively and quantitatively the impact of using excited state relaxed or unrelaxed density for the estimation of nature and characteristic of electronic excited states, we analyzed the behavior of 52 exchange correlation functionals for the prediction of density-based indexes such as those recently introduced in literature to evaluate the charge transfer distance (DCT ) (Le Bahers et al. J. Chem. Theory Comput. 2011, 7, 2498) in the case of a prototype family of push-pull dyes. Our results show that while a qualitatively consistent assessment of the nature of the excited states is obtained using either the unrelaxed or the relaxed density, from a quantitative standpoint we observe large discrepancies in the charge transfer distance for electronic transitions having substantial CT character. This behavior is independent of nature of the exchange-correlation functional used. © 2018 Wiley Periodicals, Inc.

Cationic (Charge Shift) Exciplexes.

Of the many known examples of exciplexes, those formed from bimolecular encounter between a cationic, excited state electron acceptor and a neutral donor in fluid media have not been previously reported. We now show that emissive exciplexes formed from excited N-methyl isoquinolinium cation (NMiQ+) with alkyl benzene donors are readily detected in acetonitrile. These cationic exciplexes result in a charge shift (A+* + D → A•D•+) with no net change in charge, which differs fundamentally from the charge-generation of conventional exciplex formation (A* + D → A•-D•+). We find that cationic and conventional exciplexes show similar trends, e.g., bathochromic shifts and decreases in fluorescence quantum yields with decreasing oxidation potentials of the donors. In the presented examples of NMiQ+ exciplexes, the fluorescence quantum yield decreases by a factor of 30 and the radiative rate constant by 6.6 as the fractional CT character of the exciplex increases from ∼0.79 to ∼0.95. Interestingly, the electronic coupling matrix elements for the NMiQ+ exciplexes, derived from a correlation of the radiative rate constants with the average emission frequencies, are similar to those of related conventional exciplexes, in spite of the absence of Coulombic stabilization in the cationic exciplexes.

Design Strategy for Ag(I)-Based Thermally Activated Delayed Fluorescence Reaching an Efficiency Breakthrough

A design strategy for the development of Ag(I)-based materials for thermally activated delayed fluorescence (TADF) is presented. Although Ag(I) complexes usually do not show TADF, the designed material, Ag(dbp)(P2-nCB) [dbp = 2,9-di-n-butyl-1,10-phenanthroline, and P2-nCB = nido-carborane-bis(diphenylphosphine)], shows a TADF efficiency breakthrough exhibiting an emission decay time of τ(TADF) = 1.4 μs at a quantum yield of ΦPL = 100%. This is a consequence of three optimized parameters. (i) The strongly electron-donating negatively charged P2-nCB ligand destabilizes the 4d orbitals and leads to low-lying charge (CT) states of MLL′CT character, with L and L′ being the two different ligands, thus giving a small energy separation between the lowest singlet S1 and triplet T1 state of ΔE(S1–T1) = 650 cm–1 (80 meV). (ii) The allowedness of the S1 → S0 transition is more than 1 order of magnitude higher than those found for other TADF metal complexes, as shown experimentally and by time-dependent density functi...

Coherent Dynamics of Mixed Frenkel and Charge-Transfer Excitons in Dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene Thin Films: The Importance of Hole Delocalization.

Charge-transfer states in organic semiconductors play crucial roles in processes such as singlet fission and exciton dissociation at donor/acceptor interfaces. Recently, a time-resolved spectroscopy study of dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene (DNTT) thin films provided evidence for the formation of mixed Frenkel and charge-transfer excitons after the photoexcitation. Here, we investigate optical properties and excitation dynamics of the DNTT thin films by combining ab initio calculations and a stochastic Schrödinger equation. Our theory predicts that the low-energy Frenkel exciton band consists of 8-47% CT character. The quantum dynamics simulations show coherent dynamics of Frenkel and CT states in 50 fs after the optical excitation. We demonstrate the role of charge delocalization and localization in the mixing of CT states with Frenkel excitons as well as the role of their decoherence.

Synthesis, characterization and spectral properties of new, highly fluorescent, 4-hydroxythiazoles

Eight substituted 2-aryl-4-hydroxy-5-(2′-hydroxyphenyl)-1,3-thiazoles have been prepared and their fluorescence properties have been investigated under neutral and alkaline conditions in solutions of various organic solvents. From the comparison with analogous 4-hydroxy-2,5-diphenyl-1,3-thiazole it is clear that both in neutral as well as in the deprotonated state the presence of the 2′-hydroxy group substantially (2–4 times) enhances fluorescence quantum yields (Φ) – most probably due to formation of an intramolecular hydrogen bond. Introduction of an electron withdrawing substituent into the 2-aryl group (2-pyridyl and 4-trifluormethylphenyl derivatives) further enhances Φ up to 0.93 (in dioxane). Upon deprotonation of the 4-hydroxy group a large bathochromic shift of the absorption (Δλmax ≈ 70 nm) as well as emission (Δλem ≈ 110 nm) bands occurs and the Φ-s are typically between 0.3 and 0.7. On the basis of quantum chemical calculations and spectral results, a hydrogen bond interaction between two hydroxyl groups is obvious. The first absorption band of all studied compounds corresponds to π–π* HOMO–LUMO transition possessing a CT character.

Electronic Structure Description of a Doubly Oxidized Bimetallic Cobalt Complex with Proradical Ligands.

The geometric and electronic structure of a doubly oxidized bimetallic Co complex containing two redox-active salen moieties connected via a 1,2-phenylene linker was investigated and compared to an oxidized monomeric analogue. Both complexes, namely, CoL(1) and Co2L(2), are oxidized to the mono- and dications, respectively, with AgSbF6 and characterized by X-ray crystallography for the monomer and by vis-NIR (NIR = near-infrared) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and density functional theory (DFT) calculations for both the monomer and dimer. Both complexes exhibit a water molecule coordinated in the apical position upon oxidation. [CoL(1)-H2O](+) displays a broad NIR band at 8500 cm(-1) (8400 M(-1) cm(-1)), which is consistent with recent reports on oxidized Co salen complexes (Kochem, A. et al., Inorg. Chem., 2012, 51, 10557-10571 and Kurahashi, T. et al., Inorg. Chem., 2013, 52, 3908-3919). DFT calculations predict a triplet ground state with significant ligand and metal contributions to the singularly occupied molecular orbitals. The majority (∼75%) of the total spin density is localized on the metal, highlighting both high-spin Co(III) and Co(II)L(•) character in the electronic ground state. Further oxidation of CoL(1) to the dication affords a low-spin Co(III) phenoxyl radical species. The NIR features for [Co2L(2)-2H2O](2+) at 8600 cm(-1) (17 800 M(-1) cm(-1)) are doubly intense in comparison to [CoL(1)-H2O](+) owing to the description of [Co2L(2)-2H2O](2+) as two non-interacting oxidized Co salen complexes bound via the central phenylene linker. Interestingly, TD-DFT calculations predict two electronic transitions that are 353 cm(-1) apart. The NIR spectrum of the analogous Ni complex, [Ni2L(2)](2+), exhibits two intense transitions (4890 cm(-1)/26 500 M(-1) cm(-1) and 4200 cm(-1)/21 200 M(-1) cm(-1)) due to exciton coupling in the excited state. Only one broad band is observed in the NIR spectrum for [Co2L(2)-2H2O](2+) as a result of the contracted donor and acceptor orbitals and overall CT character.

Excited State Features and Dynamics in a Distyrylbenzene-Based Mixed Stack Donor-Acceptor Cocrystal with Luminescent Charge Transfer Characteristics.

Combined structural, photophysical, and quantum-chemical studies at the quantum mechanics/molecular mechanics (QM/MM) level precisely reveal the structure-property relationships in a mixed-stack donor-acceptor cocrystal, which displays vibronically structured fluorescence, strongly red-shifted against the spectra of the parent donor and acceptor, with high quantum yield despite the pronounced CT character of the emitting state. The study elucidates the reasons for this unusual combination, quantifies the ordering and nature of the collective excited singlet and triplet state manifold, and details the deactivation pathways of the initially created Franck-Condon state.

A negligible CT character of the lowest excited state of a novel complex of zinc tetraphenylporphyrin with axially bonded 2-(4-methoxy-trans-styryl)quinoline-1-oxide ligand: Experimental studies and TD DFT/CAM B3LYP [6-31G(d,p)] calculations

Abstract The crystal structure and photophysical behavior of the novel (1:1) ZnTPP–MSQNO complex composed of ZnTPP unit with axially bonded 2-(4-methoxy-trans-styryl)quinoline-1-oxide ligand (MSQNO) has been extensively investigated both in solution and in the solid state. The single-crystal X-ray measurements, stationary absorption and emission spectra and the time-resolved fluorescence spectroscopy combined with TD DFT/CAM B3LYP [6-31G(d,p)] calculations were employed. The crystal structure is characterized by the centrosymmetric triclinic unit cell, space group P 1 ¯ . Zinc atom in the studied complex is pulled out 0.365 A from the porphyrin macrocycle and the MSQNO ligand occurs in the anti-rotameric form of the trans-isomer. The complex formation in the solution is confirmed by the appropriate red shift of the Qx and Qy band in the absorption spectrum in toluene, which is in a good agreement with the results obtained by theoretical calculations. We have found that effective mixing of electronic configurations of the locally excited states with those of the charge transfer type leads to a negligible CT nature of the S1 state of ZnTPP–MSQNO complex. We also hypothesized, that due to an overlap of the absorption spectrum of MSQNO and ZnTPP in the Soret band region, the electronic coupling becomes possible and the nonradiative energy transfer process as an additional deactivation channel may take place. An unusually short lifetime (0.6 ns) was revealed for the solid complex, while in toluene (1.5 ns) and in n-propanol (2.7 ns), they shown to be several times longer.

Binding and fluorescence enhancing behaviour of phenanthrimidazole with different phases of TiO2

Photoinduced intramolecular charge transfer (ICT) in a series of a newly synthesized 1H-phenanthro[9,10-d]imidazoles containing electron donor–acceptor fragments have been studied. The effect of solvents on the fluorescence spectra indicates the CT character of emitting singlet states and analysis of CT fluorescence accounts the electron transfer in the Marcus inverted region. Nanocrystalline anatase and rutile phases of TiO2 were obtained by the sol–gel method, characterized by X-ray diffraction, high resolution scanning electron microscopy, transmission electron microscopy and energy dispersive, UV-visible diffuse reflectance, and solid photoluminescence spectroscopies. TiO2 Hombikat was supplied by fluka. TiO2 P25 was a gift from Degussa. Absorption, fluorescence and lifetime spectral studies, and cyclic voltammetric analysis have been employed to investigate the interaction of TPIN with TiO2 (A), TiO2 (H), TiO2 (P25) and TiO2 (R). The fluorescence of TPIN is efficiently quenched by TiO2 (A), TiO2 (H) and TiO2 (P25) nanoparticles owing to charge injection from the excited singlet state of TPIN to the conduction band of the TiO2 nanoparticles. However, TiO2 (R) enhances the fluorescence due to lowering of LUMO and HOMO levels of TPIN.

Understanding the photophysical properties of coumarin-based Pluronic–silica (PluS) nanoparticles by means of time-resolved emission spectroscopy and accurate TDDFT/stochastic calculations

The photophysical properties of two 7-aminocoumarin molecules with flexible and rigid alkyl moieties at the 7-nitrogen atom have been investigated in ethanol and in Pluronic-silica nanoparticles (PluS NPs) by means of time-resolved emission spectroscopy (TRES) and time-dependent density functional theory (TDDFT). Although the two coumarin derivatives have very different photophysical properties in solution, they show quite similar photophysical behaviour when embedded into the NPs, where an increase in the fluorescence quantum yield of about 10 times was observed for the more flexible molecule. TDDFT calculations employing long-range corrected functionals and with proper account of environmental effects reveal that the formation of an accessible twisted-intramolecular charge transfer state (TICT) is possible for 7-aminocoumarin molecules with flexible alkyl groups in fluid solution, where a conical intersection between the S1 and S0 states is observed at a dihedral angle of about 80°. The excited state dynamics of the population density of this reaction coordinate in ethanol and in silica NPs investigated through the resolution of a generalized Smoulochowsky equation shows that this deactivation mechanism is drastically hampered in a silica matrix, in good agreement with experimental evidence. Steady state and time resolved measurements also suggest that at high concentration for both the dyes intermolecular interactions into the silica matrix lead to fluorescence quenching. TDDFT/PCM calculations clearly indicate that the strong quenching and red shift observed is imputable to the formation of excimers with CT character after absorption of the monomeric species.

Synthesis, photophysics and reverse saturable absorption of bipyridyl platinum(ii) bis(arylfluorenylacetylide) complexes

A series of Pt(II) bipyridyl complexes with different aryl substituents (Ar = naphthyl (1a), anthryl (1b), pyrenyl (1c) and phenothiazyl (1d)) on the fluorenylacetylide ligands are synthesized and investigated. The influence of the aryl substituent on the photophysics of these complexes is systematically investigated by spectroscopic methods and simulated by time dependent density functional theory (TD-DFT). All complexes exhibit ligand-centered (1)π,π* transitions significantly admixed with the metal-to-ligand charge transfer ((1)MLCT)/ligand-to-ligand charge transfer ((1)LLCT) transitions in the UV and blue spectral region, and broad, structureless (1)MLCT/(1)LLCT absorption bands in the visible spectral region. All complexes are emissive in solution at room temperature, with the fluorescence originating predominantly from the (1)MLCT/(1)LLCT states. The triplet emitting state is dominated by the (3)π,π* state localized on the fluorenylacetylide motif and mixed with some (3)ML'CT character (metal-to-fluorenylacetylide ligand charge transfer) for 1a, 1b and 1d. For 1c, the phosphorescence predominantly originates from the pyrene localized (3)π,π* state. The variation in the photophysical properties is related to the twisting angle of the aryl substituent from the fluorenyl plane, which defines the conjugation between the substituents and fluorenylacetylide ligands and, consequently, alters the energy and intensity of absorption and emission in these complexes. also exhibit broadband triplet excited-state absorption in the visible spectral region. Therefore, they show strong reverse saturable absorption at 532 nm for nanosecond laser pulses as demonstrated by the nonlinear transmission experiment.

Effects of Hydrogen Bonding on the Transition Properties of Ethanol–Water Clusters: A TD-DFT Study

In this work, time-dependent density functional theory method was used to study the electronic transitions of hydrogen-bonded ethanol–water complexes Dimer-I, Dimer-II and Trimer. The intermolecular hydrogen bonds H1···O1 and O···H2 were demonstrated by the optimized geometric structures of the three hydrogen-bonded ethanol–water complexes. It is demonstrated that the S1-state electronic transitions for ethanol monomer and the hydrogen-bonded complex Dimer-I (through HB-I) should be of LE nature on the ethanol molecule, while those of complexes Dimer-II and Trimer should be of CT character from the hydrogen-bonded water molecule (through HB-II) to the ethanol moiety. The different electronic transition types should be the reasons for the tiny redshift of the S1-state electronic energy for Dimer-I and the large blueshifts for Dimer-II and the Trimer compared with that of the ethanol monomer.

Synthesis and Photophysical Properties of Cyclometalated Platinum(II) 1,2-Benzenedithiolate Complexes and Heterometallic Derivatives Obtained from the Addition of [Au(PCy3)]+ Units

The cyclometalated compounds [Pt(C^N)(HC^N)Cl] [HC^N = 2-phenylpyridine (Hppy; 1a), 1-(4-tert-butylphenyl)isoquinoline (Htbpiq; 1b)] react with 1,2-benzenedithiol, t-BuOK, and Bu(4)NCl in a 1:1:2:1 molar ratio in CH(2)Cl(2)/MeOH to give the complexes Bu(4)N[Pt(C^N)(bdt)] [bdt = 1,2-benzenedithiolate; C^N = ppy (Bu(4)N2a), tbpiq (Bu(4)N2b)]. In the absence of Bu(4)NCl, the same reactions afford solutions of K2a and K2b, which react with [AuCl(PCy(3))] to give the neutral heterometallic derivatives [Pt(C^N)(bdt){Au(PCy(3))}] [C^N = ppy (3a), tbpiq (3b)]. The cationic derivatives [Pt(C^N)(bdt){Au(PCy(3))}(2)]ClO(4) [C^N = ppy (4a), tbpiq (4b)] are obtained by reacting 3a and 3b with acetone solutions of [Au(OClO(3))(PCy(3))]. The crystal structures of 3b and 4b reveal the formation of short Pt···Au metallophilic contacts in the range 2.929-3.149 Å. Complexes 3b, 4a, and 4b undergo dynamic processes in solution that involve the migration of the [Au(PCy(3))](+) units between the S atoms of the dithiolate. Complexes Bu(4)N2a and 2b display a moderately solvatochromic band in their electronic absorption spectra that can be ascribed to a transition of mixed ML'CT/LL'CT character (M= metal; L = bdt; L' = C^N; CT = charge transfer), while their emissions are assignable to transitions of the same orbital parentage but from triplet excited states. The successive addition of [Au(PCy(3))](+) units to the anions 2a and 2b results in an increase in the absorption and emission energies attributable to lower highest occupied molecular orbital energies. Additionally, the characteristics of the absorption and emission spectra of the heterometallic derivatives indicate a gradual loss of LL'CT character in the involved electronic transitions, with a concomitant increase of the L'C and ML'CT contributions.

Photoinduced intramolecular charge transfer phenomena in 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid

A donor acceptor substituted aromatic system 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid (DMAPPDA) has been synthesized and its spectral properties have been explored on the basis of steady state absorption and fluorescence spectroscopy. Spectral features point largely towards a possible occurrence of photoinduced intramolecular charge transfer process from the donor NMe2 group to the acceptor acid group. Solvent dependency of the large Stokes’ shifted emission band and the calculated large excited state dipole moment support the polar character of the charge transfer excited state. Quantum yield calculations and effect of addition of acid and base on the steady state spectra were also performed to further scrutinize the excited state CT character.

Synthesis of 1-(1-ferrocenylethyl)-pyridinium chloride and its hybrid materials with lindquist-type polyoxometalates

A new ferrocene derivative, 1-(1-ferrocenylethyl)-pyridinium (fep = CpFeCp–CH(CH 3)–Py +) chloride, and two charge-transfer salts (CTSs) based on the cationic fep donor and Lindqvist-type polyoxometalate acceptors, [fep] 2[Mo 6O 19] ( 1) and [fep] 2[W 6O 19] ( 2), were synthesized. fepCl was characterized by elemental analysis, IR spectroscopy and 1H NMR and the two CTSs were characterized by elemental analysis, IR spectroscopy, UV–vis diffuse reflectance spectrum, cyclic voltammetry, fluorescence spectrum and single crystal X-ray diffraction. X-ray crystallographic studies of the brownish red CTSs 1 and 2 reveal that they are isostructural and crystallize in the monoclinic space group P2 1/ n. In salts 1– 2, fep and polyoxoanions are cocrystallized by Coulombic forces, and there also exist the complex C–H⋯π and π⋯π stacking interactions between the adjacent fep cations and C–H⋯O hydrogen bonds between the adjacent fep cations and polyanions. The UV–vis diffuse reflectance spectra indicate the presence of a broad charge-transfer band between 500 and 850 nm for 1– 2, and CT character of 1 and 2 is also confirmed by the Mulliken correlation between the CT transition energies and the reduction potentials of the polyoxometalate acceptors.

Rhomboidal Heterometallic Alkynyl Based Pt2Cd2 Clusters: Structural, Photophysical, and Theoretical Studies

Reactions between [Pt(C[triple bond]CR)(4)](2-) (R = Tol a, C(6)H(4)OMe-4 b, C(6)H(4)OMe-3 c) and Cd(2+) depend on the media and the alkynyl substituent, leading to the formation of yellow tetranuclear solvate complexes [Pt(C[triple bond]CR)(4)Cd(acetone)](2) 1a,b(acetone)(2) and [Pt(C[triple bond]CC(6)H(4)OMe-3)(4)Cd(dmso)](2) 1c(dmso)(2) or white polymeric solvate-free species [Pt(C[triple bond]CR)(4)Cd](x) 1'a-c. Treatment of 1a,b(acetone)(2) or 1'a-c with N-donor ligands affords a series of tetranuclear clusters [Pt(C[triple bond]CR)(4)CdL](2) (L = py; 2a-c. R = Tol; L = NC(5)H(4)CH(3)-4 3, NC(5)H(4)CF(3)-4 4, pzH 5). X-ray crystallographic studies reveal that, in the tolyl complexes (2a, 4, and 5), the Cd-L(2+) unit is closely bonded to one Pt-C(alpha)(acetylide) bond (Pt-Cd = 2.7, Cd-C(alpha) approximately 2.48 A), and the resulting "Pt(C[triple bond]CTol)(4)CdL" unit dimerizes by two additional eta(2)-Cd-acetylide and a weaker Pt...Cd bonding interaction leading to a planar unsymmetrical rhomboidal metal core. By contrast, the m-methoxyphenyl derivatives (2c, 1c(dmso)(2)) form symmetrical Pt(2)Cd(2) cores, with each Cd bonded (coordination number, C.N. = 5) to the incoming ligand (pyridine 2c, dmso 1c(dmso)(2)) and four Pt-C(alpha) bonds (Pt-Cd approximately 2.85; Cd-C(alpha) 2.470(10)-2.551(5) A) of different Pt(II) fragments. Evidence of ligand dissociation was found for the solvate (1a,b(acetone)(2), 1c(dmso)(2)) and NC(5)H(4)CF(3)-4 (4) derivatives by NMR and UV-vis absorption spectra. All tetranuclear aggregates exhibit bright blue to green luminescence in the solid state. Time-dependent density functional theory (TD-DFT) calculations were performed to shed light on the nature of the electronic transitions. In the solvate 1a,b(acetone)(2) and 1c(dmso)(2), emissions have been assigned to a platinum-alkynyl to cadmium charge transfer ((3)MLM'CT), mixed with some intraligand (3)IL(C[triple bond]CR) character. In the imine derivatives 2-5, they are suggested to come from an excited state of large Pt(d)/piC[triple bond]CR-->pi*(imine) MLL'CT character, mixed with some Pt(d)/pi(C[triple bond]CR)-->Pt(2)Cd(2)/pi*C[triple bond]CR (ML'M'CT) contribution.

Structural and Luminescence Studies on π···π and Pt···Pt Interactions in Mixed Chloro-Isocyanide Cyclometalated Platinum(II) Complexes†

[Pt(bzq)Cl(CNR)] [bzq = benzoquinolinate; R = tert-butyl ((t)Bu 1), 2-6-dimethylphenyl (Xyl 2), 2-naphthyl (2-Np 3)] complexes have been synthesized and structurally and photophysically characterized. 1 was found to co-crystallize in two distinct pseudopolymorphs: a red form, which exhibits an infinite 1D-chain ([1](infinity)) and a yellow form, which contains discrete dimers ([1](2)), both stabilized by interplanar pi...pi (bzq) and short Pt...Pt bonding interactions. Complex 3, generated through the unexpected garnet-red double salt isomer [Pt(bzq)(CN-2-Np)(2)][Pt(bzq)Cl(2)] 4, crystallizes as yellow Pt...Pt dimers ([3](2)), while 2 only forms pi...pi (bzq) contacting dimers. Their electronic absorption and luminescence behaviors have been investigated. According to Time-Dependent Density Functional Theory (TD-DFT) calculations, the lowest-lying absorption (CH(2)Cl(2)) has been attributed to combined (1)ILCT and (1)MLCT/(1)ML'CT (L = bzq, L' = CNR) transitions, the latter increasing from 1 to 3. In solid state, while the yellow form [1](2) exhibits a green (3)MLCT unstructured emission only at 77 K, the 1-D form [1](infinity) displays a characteristic low-energy red emission (672 nm, 298 K; 744 nm, 77 K) attributed to a mixed (3)MMCT [d(sigma*)-->p(sigma)]/(3)MMLCT [dsigma*(M(2))-->sigma(pi*)(bzq)] excited state. However, upon exposure to standard atmospheric conditions, [1](infinity) shows an irreversible change to an orange-ochre solid, whose emissive properties are similar to those of the crude 1. Complexes 2 and 3 (77 K) exhibit a structured emission from discrete fragments ((3)LC/(3)MLCT), whereas the luminescence of the garnet-red salt 4 is dominated by a low energy emission (680 nm, 298 K; 730 nm, 77 K) arising from a (3)MMLCT excited state. Solvent (CH(2)Cl(2), toluene, 2-MeTHF and CH(3)CN) and concentration-dependent emission studies at 298 K and at 77 K are also reported for 1-3. In CH(2)Cl(2) solution, the low phosphorescent emission band is ascribed to bzq intraligand charge transfer (3)ILCT mixed with metal-to-ligand (L = bzq, L' = CNR) charge transfer (3)MLCT/(3)ML'CT character with the Pt to CNR contribution increasing from 1 to 3, according to computational studies.

Synthesis and fluorescence properties of dimethylaminonaphthalene–deoxyuridine conjugates as polarity-sensitive probes

The design of probes for monitoring various structures and dynamics of DNA and its surroundings is an important step in understanding biological events accompanying interbiomolecular interaction. We have developed novel fluorescent nucleosides in which the uracil base and the fluorophore are tethered by rigid linkers. They show unique absorption and fluorescence emission spectra. Nucleoside 2 is a fluorophore with high CT character and the fluorescence is very sensitive to solvent polarity. Nucleoside 3 shows absorption and emission maxima with longer wavelength due to extension of the DAN-conjugate system. These fluorophore–deoxyuridine conjugates with unique fluorescence properties would work as reporter probes sensitive to the change in microenvironment around specific sites of DNA.

Push‐Pull Oligomers with 2,2‐Dicyanovinyl Groups as Electron Acceptors

AbstractThree conjugated oligomer series with terminal donor–acceptor substitution were studied: oligo(1,4‐phenylenevinylene)s DAOPVs 4a–d (n = 1–4), oligo(1,4‐phenyleneethynylene)s DAOPEs 6a–d (n = 1–4) and oligo(2,5‐thienyleneethynylene)s DAOTEs 8a–e (n = 1–5). Dialkylamino or methoxy groups served as electron donors and 2,2‐dicyanovinyl groups as strong electron acceptors. The push‐pull effect polarizes the molecular chains – an effect which is documented by the splitting of the 13C chemical shifts of two carbon atoms of the double or triple bonds in the chain. For higher oligomers (n ≥ 3), the effect is mainly localized at the chain ends. The long‐wavelength absorption results in a charge‐transfer band which loses gradually its CT character since the intramolecular charge transfer (ICT) declines with increasing numbers n of repeat units (increasing chromophore extension, increasing distance D–A). As a consequence, theDAOPVs 4a–d and the DAOPEs 6a–d represent hypsochromic series, for which the λmax values decrease steadily from n = 1 to n = 4. This is also true for the DAOTE series 8a–e, but contrary to 4a–d and 6a–d the decrease is very small in the beginning [λmax(1) – λmax(2) = 1 nm] and grows with increasing n to λmax(4) – λmax(5) = 29 nm. Thus, series 8a–e represents an until now unknown type of conjugated push‐pull oligomers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)