Vibronic Fine Structure Research Articles

UV Absorption Spectroscopy of the Conformer-Dependent Reactivity of the Four Carbon Criegee Intermediate of Methyl Vinyl Ketone Oxide: An Ab initio Quantum Dynamics Study.

An extended theoretical analysis of the photodissociation dynamics of the four-carbon Criegee intermediate (CH2═CH(CH3)COO) or methyl vinyl ketone oxide, which has four conformers, following excitation to the B state, is presented. Our analysis relies on multireference electronic wave functions combined with a wavepacket propagation treatment for the two coupled B1A' and C1A' electronic states and two nuclear degrees of freedom. For each conformer, the 2D model depends on potential energy surfaces (PESs) along the O-O and C-O-O bending modes for the two lowest excited states, B1A' and C1A', and is sufficiently accurate to reproduce the experimental B1A' ← X1A' absorption spectrum with unprecedented accuracy. It is found that the roles of each conformer are essential in producing a cumulative spectrum, which is close to the recent experimental spectrum. The anti-trans and anti-cis conformers make contributions at the longer and shorter wavelengths of the cumulative spectrum, respectively, while the syn-cis and syn-trans conformers have contributions in the middle wavelength range of the cumulative spectrum of MVK-oxide. The existence of a deep well for each conformer on the PESs of the (diabatic) B state causes a considerable amount of the wavepacket to be reflected by the B state wells, which can explain the oscillatory structures appearing in the long wavelength range of 360-480 nm of the spectrum. The weakly avoided crossings between the B-state and C-state PESs of each conformer appearing within the range of 2.80-3.08 eV excitation energy cause considerable disturbance in the vibronic fine structure of the bands. The results give novel insight into the complex interactions governing this intriguing process.

Mixed Microscopic Eu2+ Occupancies in the Next‐Generation Red LED Phosphor Sr[Li2Al2O2N2]:Eu2+ (SALON:Eu2+)

AbstractRed‐emitting narrow‐band phosphors are of utmost importance for next‐generation white‐light phosphor‐converted light‐emitting diodes (pc‐wLEDs) for improved efficacy and optimized correlated color temperatures. A promising representative crystallizing in an ordered variant of the UCr4C4 structure type is Sr[Li2Al2O2N2]:Eu2+ (SALON:Eu2+) emitting at a desirable wavelength of 614 nm. Despite an expected eightfold coordination of the Eu2+ ions by four N3− and O2− ions, respectively, the exact local coordination symmetry and a 1:1 ratio between the two types of ligands is not straightforwardly proven by X‐ray diffraction. Low‐temperature luminescence spectroscopy in conjunction with ligand field theory are powerful alternatives to resolve local features of Eu2+ as its excited 4f65d1 configuration reacts sensitively to the polarity of the ligands. The dominant emission at 614 nm shows pronounced vibronic fine structure at 10 K. In addition, weak emission bands can be resolved at 570 and 650 nm even at a low doping concentration of 0.5 mol% and are assigned to Eu2+ ions being eightfold coordinated by N3− and O2− ions in a ratio different from 1:1. Due to the feature of vierer ring‐type channels in SALON:Eu2+, those Eu2+ centers are sufficiently close for mutual energy transfer, which is characterized by time‐resolved luminescence at 10 K.

Photochemical properties of a potential interstellar dust precursor: the electronic spectrum of Si3O2.

Silicon oxide compounds are considered as precursors for silicon-based interstellar dust grains which consist mainly of silica and silicates. Knowledge of their geometric, electronic, optical, and photochemical properties provides crucial input for astrochemical models describing the evolution of dust grains. Herein, we report the optical spectrum of mass-selected Si3O2+ cations recorded in the 234-709 nm range by means of electronic photodissociation (EPD) in a quadrupole/time-of-flight tandem mass spectrometer coupled to a laser vaporization source. The EPD spectrum is observed predominantly in the lowest-energy fragmentation channel corresponding to Si2O+ (loss of SiO), while the higher-energy Si+ channel (loss of Si2O2) provides only a minor contribution. The EPD spectrum exhibits two weaker unresolved bands A and B near 26 490 and 34 250 cm-1 (377.5 and 292 nm) and a strong transition C with a band origin at 36 914 cm-1 (270.9 nm) which shows vibrational fine structure. Analysis of the EPD spectrum is guided by complementary time-dependent density functional theory (TD-DFT) calculations at the UCAM-B3LYP/cc-pVTZ and UB3LYP/cc-pVTZ levels to determine structures, energies, electronic spectra, and fragmentation energies of the lowest-energy isomers. The cyclic global minimum structure with C2v symmetry determined previously by infrared spectroscopy can explain the EPD spectrum well, with assignments of bands A-C to transitions from the 2A1 ground electronic state (D0) into the 4th, 9th, and 11th excited doublet states (D4,9,11), respectively. The vibronic fine structure of band C is analyzed by Franck-Condon simulations, which confirm the isomer assignment. Significantly, the presented EPD spectrum of Si3O2+ corresponds to the first optical spectrum of any polyatomic SinOm+ cation.

Macrocyclic Donor-Acceptor Dyads Composed of Oligothiophene Half-Cycles and Perylene Bisimides.

A series of donor‐acceptor (D−A) macrocyclic dyads consisting of an electron‐poor perylene bisimide (PBI) π‐scaffold bridged with electron‐rich α‐oligothiophenes bearing four, five, six and seven thiophene units between the two phenyl‐imide substituents has been synthesized and characterized by steady‐state UV/Vis absorption and fluorescence spectroscopy, cyclic and differential pulse voltammetry as well as transient absorption spectroscopy. Tying the oligothiophene strands in a conformationally fixed macrocyclic arrangement leads to a more rigid π‐scaffold with vibronic fine structure in the respective absorption spectra. Electrochemical analysis disclosed charged state properties in solution which are strongly dependent on the degree of rigidification within the individual macrocycle. Investigation of the excited state dynamics revealed an oligothiophene bridge size‐dependent fast charge transfer process for the macrocyclic dyads upon PBI subunit excitation.

Signatures of coherent vibronic exciton dynamics and conformational control in the two-dimensional electronic spectroscopy of conjugated polymers.

Two-dimensional electronic spectroscopy (2DES) signals for homo-oligomer J-aggregates are computed, with a focus on the role of structural change induced by low-frequency torsional modes, along with quasi-stationary trapping effects induced by high-frequency polaronic modes. To this end, a model system is derived from an ab initio parametrized site-based Hamiltonian for oligothiophenes [Binder et al., Phys. Rev. Lett., 2018, 120, 227401]. To obtain a compact representation, we introduce a collective lattice mode whose vibronic coupling depends nonlinearly on the exciton density. As a result, an N-site model with a single polaronic mode and a single torsional mode is obtained. Furthermore, a quantum-classical treatment is employed where the torsional mode is treated within a mean-field Ehrenfest/Langevin approximation. 2D electronic spectra are computed using the equation-of-motion phase-matching approach (EOM-PMA) within a wavefunction description. It is seen that the spectra combine the vibronic fine structure, due to the polaronic mode, and a dynamic Stokes shift, due to torsional relaxation. The signatures of the coherent effects and adiabatic evolution in the 2DES signals are discussed.

Resolving Jahn-Teller induced vibronic fine structure of silicon vacancy quantum emission in silicon carbide

Point defects in semiconductors are promising single-photon emitters (SPEs) for quantum computing, communication, and sensing applications. However, factors such as emission brightness, purity. and indistinguishability are limited by interactions between localized defect states and the surrounding environment. Therefore, it is important to map the full emission spectrum from each SPE, to understand the complex interplay between the different defect configurations, their surroundings, and external perturbations. Herein, we investigate a family of regularly spaced sharp luminescence peaks appearing in the near-infrared portion of photoluminescence (PL) spectra from $n$-type 4H-SiC samples after irradiation. This periodic emitter family, labeled the L lines, is only observed when the zero-phonon line signatures of the negatively charged Si vacancy (so-called V lines) are present. The L lines appear with $1.45\phantom{\rule{0.28em}{0ex}}\mathrm{meV}$ and $1.59\phantom{\rule{0.28em}{0ex}}\mathrm{meV}$ energy spacing after H and He irradiation and increase linearly in intensity with fluence---reminiscent of the intrinsic defect trend. Furthermore, we monitor the dependence of the L-line emission energy and intensity on heat treatments, electric field strength, and PL collection temperature, discussing these data in the context of the L lines. Based on the strong similarity between the irradiation, electric field, and thermal responses of the L and V lines, the L lines are attributed to the Si vacancy in 4H-SiC. The regular and periodic appearance of the L lines provides strong arguments for a vibronic origin explaining the oscillatory multipeak spectrum. To account for the small energy separation of the L lines, we propose a model based on rotations of distortion surrounding the Si vacancy driven by a dynamic Jahn-Teller effect.

Highly Efficient Deep Blue Luminescence of 2-Coordinate Coinage Metal Complexes Bearing Bulky NHC Benzimidazolyl Carbene.

The structural, photophysical and electrochemical properties of three luminescent 2-coordinate coinage metal (i.e., M = Cu, Ag, Au) complexes bearing a sterically bulky benzimidazolyl carbene, 1,3-bis(2,6-diisopropylphenyl)-1-H-benzo[d]imidazol-2-ylidene (BZI), and carbazolide (Cz) as the anionic ligand were investigated. All the complexes emit in the deep blue region (~430 nm) with relatively narrow spectra (full width at half maximum = 44 nm, 2,300 cm−1) characterized by vibronic fine structure in nonpolar media (methylcyclohexane at room temperature), and with high photoluminescence quantum yields (ΦPL > 80%) and radiative rate constants (kr ~ 7.8 × 105 s−1). The luminescence is solvatochromic, undergoing a red-shift in a polar solvent (CH2Cl2) at room temperature that are accompanied by a decrease in quantum yields (ΦPL < 23%) and radiative rate constants (kr < 4.0 × 104 s−1), whereas the non-radiative rate constants remain nearly constant (knr ~ 1.0 × 105 s−1). The radiative rate is controlled via thermally assisted delayed fluorescence (TADF) and temperature-dependent luminescence studies of the gold complex (AuBZI) in methylcyclohexane solution reveal an energy difference between the lowest singlet and triplet excited states of 920 cm−1. An organic light-emitting diode (OLED) fabricated using AuBZI as a luminescent dopant has an external quantum efficiency of 12% and narrow, deep-blue emission (CIE = 0.16, 0.06).

Uranyl Tricarballylate Triperiodic and Nanotubular Species. Counterion Control of Nanotube Diameter.

Tricarballylic acid (propane-1,2,3-tricarboxylic acid, H3 tca) was reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions and in the presence of different additional cations, yielding four complexes which have been crystallographically characterized. [(UO2)2Ba(tca)2(H2O)4] (1), isomorphous to the PbII analogue previously reported, crystallizes as a triperiodic framework in which diperiodic uranyl-tca3- subunits with the hcb (honeycomb) topology are linked by carboxylate-bound BaII cations. Triperiodic polymerization is also found in [(UO2)2(tca)2Ni(cyclam)] (2) and [(UO2)2(tca)2Cu(R,S-Me6cyclam)] (3), but here the diperiodic uranyl-tca3- subunits have the sql (square lattice) topology, and the frameworks formed through bridging by NiII or CuII cations have different topologies, tcs in 2 and xww in 3. [Co(en)3][UO2(tca)]3·2H2O (4) crystallizes as a monoperiodic coordination polymer with the hcb topology and a nanotubular geometry. In contrast to the square-section nanotubules previously found in [NH4][(UO2)2Pb(tca)2(NO3)(bipy)] (bipy = 2,2'-bipyridine), those in 4 have a hexagonal section with a width of ∼7 Å. The structure-directing role of the hydrogen bonded counterions in these nanotubular species, either NH4+ located within the nanotubule cavity or [Co(en)3]3+ located outside, is discussed. Emission spectra in the solid state display the usual vibronic fine structure for 1 and 4, while uranyl emission is quenched in 3.

Structure-Directing Effects of Coordinating Solvents, Ammonium and Phosphonium Counterions in Uranyl Ion Complexes with 1,2-, 1,3-, and 1,4-Phenylenediacetates.

The three isomers 1,2-, 1,3-, and 1,4-phenylenediacetic acids (1,2-, 1,3-, and 1,4-pdaH2) have been used to synthesize 16 uranyl ion complexes under solvo-hydrothermal conditions and in the presence of various coligands and organic counterions. The two neutral and homoleptic complexes [UO2(1,2-pda)]·CH3CN (1) and [UO2(1,3-pda)] (2) crystallize as diperiodic assemblies with slightly different coordination modes of the ligands, but the same sql topology. Introduction of the coordinating solvents N-methyl-2-pyrrolidone (NMP) or N,N'-dimethylpropyleneurea (DMPU) in the uranyl coordination sphere produces the four complexes [UO2(1,2-pda)(DMPU)] (3), [UO2(1,3-pda)(NMP)] (4), [UO2(1,4-pda)(NMP)] (5), and [UO2(1,4-pda)(DMPU)] (6), which are either monoperiodic (4) or diperiodic species with the fes (3 and 5) or 3,4L13 (6) topology. The presence of dimethylammonium cations is associated with the formation of ladder-like monoperiodic polymers with the 1,2 isomer in the complexes [H2NMe2]2[(UO2)2(1,2-pda)3]·H2O (7) and [H2NMe2]2[(UO2)2(1,2-pda)3]·3H2O (8), while a conformational change giving the 1,3 and 1,4 isomers a pincer-like geometry favors the formation of dinuclear ring subunits assembled into daisy-chain-like monoperiodic polymers in [H2NMe2]2[(UO2)2(1,3-pda)3]·0.5H2O (9), [H2NMe2]2[(UO2)2(1,4-pda)3] (10), and the mixed-ligand species [H2NMe2]2[(UO2)2(1,2-pda)(1,4-pda)2] (11). The unique complex including guanidinium cations, [C(NH2)3]2[(UO2)2(1,2-pda)3]·0.5H2O·CH3CN (12), crystallizes as a diperiodic polymer with the hcb topology. Due to differences in ligand conformations, the phosphonium-containing complexes [PPh3Me]2[(UO2)2(1,3-pda)3] (13) and [PPh4]2[(UO2)2(1,4-pda)3] (14) contain ladder-like and daisy-chain-like monoperiodic polymers, respectively, while only the latter geometry is found in the mixed-cation complexes [PPh3Me][H2NMe2][(UO2)2(1,4-pda)3]·H2O (15) and [PPh3Me][H2NMe2][(UO2)2(1,2-pda)(1,4-pda)2] (16). The influence of ligand conformation and the structure-directing effects of coligands and counterions throughout the series are discussed. The uranyl emission spectra of 14 of the complexes display the usual vibronic fine structure, the peak positions being dependent on the number of equatorial donors.

1,3‐Adamantanedicarboxylate and 1,3‐Adamantanediacetate as Uranyl Ion Linkers: Effect of Counterions, Solvents and Differences in Flexibility

Seven homo‐ or heterometallic uranyl ion complexes with 1,3‐adamantanedicarboxylic acid (H2ADC) or 1,3‐adamantanediacetic acid (H2ADA) have been synthesized under solvo‐hydrothermal conditions in the presence of different counterions and organic cosolvents, and characterized by their crystal structure and uranyl emission spectrum. [PPh3Me][UO2(ADC)(NO3)] (1) crystallizes as a simple monoperiodic chain, but [PPh4]2[(UO2)2(ADC)3]·2H2O (2) and [PPh4]2[(UO2)2(ADA)3] (3) display trough‐like monoperiodic polymers (assembled in pairs in 3) in the cavity of which the counterions are located. A similar arrangement is found in [Ni(cyclen)(H2O)][(UO2)2(ADC)3]·H2O (4). Diaxial bonding of NiII in [(UO2)2(ADC)2Ni(R,S‐Me6cyclam)(HCOO)2]·CH3CN (5) and [UO2(ADA)2Ni(R,S‐Me6cyclam)] (6) results in bridging monoperiodic uranyl‐containing subunits into neutral, diperiodic networks. [UO2(ADA)(DMPU)] (7), containing coordinated N,N′‐dimethylpropyleneurea, is also a diperiodic assembly with the common fes topological type. Except complex 6 which is non‐luminescent, all complexes give solid‐state emission spectra displaying the usual vibronic fine structure, albeit with low photoluminescence quantum yields.

Synthesis, structure, complexation, and luminescence properties of the first metal-organic curcumin compound Bis(4-triphenylsiloxy)curcumin

Abstract The synthesis and structural characterization of 1,7-bis(4-triphenylsiloxy-3-methoxy-phenyl)-1,6-heptadiene-3,5-dione (1 = Ph3SiCurcH) and 1,7-bis(4-methoxycarbonyloxy-3-methoxy-phenyl)-1,6-heptadiene-3,5-dione (2 = MeOC(O)CurcH) are reported. Compound 1 represents the first metal-organic curcumin derivative. The complexation of 1 and 2 with Cu2+ has been studied. The new copper(II) complexes (Ph3SiCurc)2Cu (3) and [MeOC(O)Curc]2Cu·4MeCN (4) have been prepared and their crystal structures determined by single crystal X-ray diffraction. Moreover, the optical properties of the solid compound 1 have been investigated in detail. The emission spectrum shows a vibronic fine structure that has been analysed in terms of Franck-Condon factors. The excitation spectrum is broad and structureless and may be interpreted in terms of an interband transition as is also confirmed by diffuse reflectance spectra. Due to the weak intermolecular interactions, an isolated-molecule model is used instead for the assignment of the transitions, which are thus characterized as S1 ↔ S0 or π* ↔ π fluorescent transitions. Despite the electric-dipole allowed nature of the transition, the quantum yield is Φ = (2.4 ± 0.3)% in agreement with other findings on curcumin derivatives.

Unraveling electronic absorption spectra using nuclear quantum effects: Photoactive yellow protein and green fluorescent protein chromophores in water.

Many physical phenomena must be accounted for to accurately model solution-phase optical spectral line shapes, from the sampling of chromophore-solvent configurations to the electronic-vibrational transitions leading to vibronic fine structure. Here we thoroughly explore the role of nuclear quantum effects, direct and indirect solvent effects, and vibronic effects in the computation of the optical spectrum of the aqueously solvated anionic chromophores of green fluorescent protein and photoactive yellow protein. By analyzing the chromophore and solvent configurations, the distributions of vertical excitation energies, the absorption spectra computed within the ensemble approach, and the absorption spectra computed within the ensemble plus zero-temperature Franck-Condon approach, we show how solvent, nuclear quantum effects, and vibronic transitions alter the optical absorption spectra. We find that including nuclear quantum effects in the sampling of chromophore-solvent configurations using ab initio path integral molecular dynamics simulations leads to improved spectral shapes through three mechanisms. The three mechanisms that lead to line shape broadening and a better description of the high-energy tail are softening of heavy atom bonds in the chromophore that couple to the optically bright state, widening the distribution of vertical excitation energies from more diverse solvation environments, and redistributing spectral weight from the 0-0 vibronic transition to higher energy vibronic transitions when computing the Franck-Condon spectrum in a frozen solvent pocket. The absorption spectra computed using the combined ensemble plus zero-temperature Franck-Condon approach yield significant improvements in spectral shape and width compared to the spectra computed with the ensemble approach. Using the combined approach with configurations sampled from path integral molecular dynamics trajectories presents a significant step forward in accurately modeling the absorption spectra of aqueously solvated chromophores.

Closed Uranyl-Dicarboxylate Oligomers: A Tetranuclear Metallatricycle with Uranyl Bridgeheads and 1,3-Adamantanediacetate Linkers.

In the presence of NH4+ and either PPh4+ or PPh3Me+ cations, 1,3-adamantanediacetic acid (H2ADA) reacts with uranyl ions under solvo-hydrothermal conditions to give the complexes [NH4]2[PPh4]2[(UO2)4(ADA)6] (1) and [NH4]2[PPh3Me]2[(UO2)4(ADA)6] (2), both of which contain a tetranuclear metallatricycle built from two 2:2 rings including convergent ligands, linked by two additional ligands in an extended conformation defining a third, larger ring. While the ammonium cations are closely associated with the 2:2 rings through triple hydrogen bonding, the large PPh4+ or PPh3Me+ cations are more loosely bound to each of the two faces of the larger ring. In contrast, the complex [H2NMe2][PPh3Me][(UO2)2(ADA)3]·H2O (3), in which dimethylammonium replaces ammonium cations, crystallizes as a two-dimensional network with honeycomb {63} topology, albeit with very distorted, elongated hexagonal cells. These and previous results show that both NH4+ and PPh4+ or PPh3Me+ cations are essential to the formation of the metallatricycle. The role of the flexibility imparted to ADA2- by the acetate arms, in comparison to the more rigid 1,3-adamantanedicarboxylate (ADC2-), is also discussed. All three complexes are luminescent, with quantum yields of 0.06, 0.06, and 0.09 for 1-3, respectively. The vibronic fine structure apparent on the emission spectra gives peak positions typical of species in which the uranyl ion is chelated by three carboxylate groups.

Luminescence behaviour and deposition of Sc2O3 thin films from scandium(III) acetylacetonate at ambient pressure

Scandium(III) oxide thin film deposition has been historically difficult to achieve without the use of vacuum-based or wet chemical systems due to precursor limitations of low vapour pressure or ambient instability. In this letter, the adoption of aerosol-assisted delivery of scandium(III) acetylacetonate has enabled the chemical vapour deposition of polycrystalline and amorphous Sc2O3 thin films at ambient pressure with high growth rates (ca. 500 nm h−1). The scandia films were intrinsically highly photoluminescent, exhibiting broad emission bands centred at 3.6 and 3.0 eV, which increased significantly in intensity upon aerobic annealing, accompanying a transition from amorphous to crystalline, while bands appearing at 2.1 and 2.3 eV seemed to occur only in the crystalline films. In addition, both amorphous and crystalline scandia films exhibited blue-green vibronic fine structure between 2.3 and 3.2 eV attributed to the electronic transition BΣ+→ΧΣ+22 in surface ⋯O−⋯O−Sc=O groups and split by a vibrational mode observed at 920±60 cm−1 by infrared spectroscopy. Band gaps of amorphous and crystalline Sc2O3 were determined to be 5.3 and 5.7 eV, respectively via diffuse reflectance. All films had high refractive indices, varying between 1.8 and 2.0 at 400 nm depending on film thickness and carrier gas used in the deposition; film thicknesses less than ca. 300 nm were observed to have a strong influence on the refractive index measured, while there was little variation for films thicker than this. The synthesis process itself is exceedingly low-cost and facile thus promising streamlined industrial scalability.

Combining the ensemble and Franck-Condon approaches for calculating spectral shapes of molecules in solution.

The correct treatment of vibronic effects is vital for the modeling of absorption spectra of many solvated dyes. Vibronic spectra for small dyes in solution can be easily computed within the Franck-Condon approximation using an implicit solvent model. However, implicit solvent models neglect specific solute-solvent interactions on the electronic excited state. On the other hand, a straightforward way to account for solute-solvent interactions and temperature-dependent broadening is by computing vertical excitation energies obtained from an ensemble of solute-solvent conformations. Ensemble approaches usually do not account for vibronic transitions and thus often produce spectral shapes in poor agreement with experiment. We address these shortcomings by combining zero-temperature vibronic fine structure with vertical excitations computed for a room-temperature ensemble of solute-solvent configurations. In this combined approach, all temperature-dependent broadening is treated classically through the sampling of configurations and quantum mechanical vibronic contributions are included as a zero-temperature correction to each vertical transition. In our calculation of the vertical excitations, significant regions of the solvent environment are treated fully quantum mechanically to account for solute-solvent polarization and charge-transfer. For the Franck-Condon calculations, a small amount of frozen explicit solvent is considered in order to capture solvent effects on the vibronic shape function. We test the proposed method by comparing calculated and experimental absorption spectra of Nile red and the green fluorescent protein chromophore in polar and non-polar solvents. For systems with strong solute-solvent interactions, the combined approach yields significant improvements over the ensemble approach. For systems with weak to moderate solute-solvent interactions, both the high-energy vibronic tail and the width of the spectra are in excellent agreement with experiments.

Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II).

Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2'-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) "cation-cation" interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with complex 4, crystallizes as a 2D network as a result of the high degree of connectivity provided by the chelating/bridging tricarboxylate ligand. Emission spectra measured in the solid state display vibronic fine structure attributable to uranyl luminescence (except for complex 5, in which emission is quenched), with variations in maxima positions associated with modifications of the uranyl ion environment.

A Joint Theoretical and Experimental Study of the Behavior of the DIDS Inhibitor and its Derivatives.

4,4'-Diisothiocyanostilbene-2,2'-disulfonic acid (DIDS) is a well-known ion-exchange inhibitor targeting cardiac functions and indirectly impeding both radio- and chemo-resistance. A joint computational and experimental study is presented to provide deeper insights into DIDS and other members of this family of compounds. To this end, we applied state-of-the-art density functional theory (DFT) and time-dependent DFT methods, in addition to measuring the optical properties. The experimental data show that such compounds are highly sensitive to their environment and that the optical properties change within as little time as 7 h. However, the optical properties of DIDS are similar in various acidic/basic environments, which were confirmed by pKa computations on both cis and trans isomers. The protonation analysis also highlights that the singly protonated form of DIDS behaves like a proton sponge compound. The experimentally observed redshift that can be seen when going from water to DMSO was reproduced solely by using the solvation model based on density, although the polarization continuum model and implicit/explicit hybrid schemes were also tested. The characteristic broadening of the absorption peak in water and the vibronic fine structure in DMSO were also reproduced thanks to vibronic coupling simulations associated with the solvent reorganization energy. For other stilbene derivatives, a correlation is found between the maximum absorption wavelength and the Hammett parameters.

Structural Variations in the Uranyl/4,4'-Biphenyldicarboxylate System. Rare Examples of 2D → 3D Polycatenated Uranyl-Organic Networks.

4,4'-Biphenyldicarboxylic acid (H2L) was reacted with uranyl ions under solvo-hydrothermal conditions with variations in the experimental procedure (organic cosolvent, presence of additional 3d-block metal cations, and N-donor species), thus giving six complexes of the fully deprotonated acid that were characterized by their crystal structure and, in most cases, their emission spectrum. The three complexes [UO2(L)(DMA)] (1), [UO2(L)(NMP)] (2), and [UO2(L)(NMP)] (3) include the cosolvent as a coligand, and they crystallize as two-dimensional (2D) assemblies, with different combinations of the chelating and bridging-bidentate carboxylate coordination modes, resulting in two different topologies. Complex 4, [Ni(bipy)3][(UO2)2(L)2(C2O4)]·H2O, includes oxalate coligands generated in situ and contains an anionic planar two-dimensional (2D) assembly with a {6(3)} honeycomb topology. The same hexagonal geometry is found in the homoleptic complexes [Ni(bipy)3][(UO2)2(L)3]·6H2O (5) and [Ni(phen)3][(UO2)2(L)3]·4H2O (6), but the large size of the hexagonal rings in these cases (∼27 Å in the longest dimension) allows 2D → three-dimensional (3D) inclined polycatenation to occur, with the two families of networks either orthogonal in tetragonal complex 5 or at an angle of 73.4° in orthorhombic complex 6. The parallel networks are arranged in closely spaced groups of two, with possible π···π stacking interactions, and as many as four rods from four parallel nets pass through each ring of the inclined family of nets, an unusually high degree of catenation. These are the second cases only of 2D → 3D inclined polycatenation in uranyl-organic species. Emission spectra measured in the solid state show the usual vibronic fine structure, with variations in intensity and positions of maxima that are not simply connected with the number of equatorial donors and the presence of additional metal cations.

Uranyl Ion Complexes with 1,1'-Biphenyl-2,2',6,6'-tetracarboxylic Acid: Structural and Spectroscopic Studies of One- to Three-Dimensional Assemblies.

1,1'-Biphenyl-2,2',6,6'-tetracarboxylic acid (H4L) was reacted with uranyl nitrate, either alone or in the presence of additional metal cations (Ni(2+), Cu(2+), Dy(3+)) under (solvo)-hydrothermal conditions, giving six complexes which were characterized by their crystal structure and, in all but one case, their emission spectrum in the solid state. [Ni(bipy)3][UO2(H2L)(H2O)]2(NO3)2·3H2O (1) crystallizes as a one-dimensional (1D), ribbon-like coordination polymer, while the homometallic complex [(UO2)2(L)(H2O)3]·H2O·CH3CN (2) and the heterometallic complexes [UO2Cu(L)(H2O)2]·H2O (3), [UO2Cu(L)(H2O)]·H2O (4), and [(UO2)5Cu4(HL)6(bipy)4]·2H2O (5) display two-dimensional (2D) arrangements. Lastly, the uranyl-lanthanide heterometallic complex [(UO2)8Dy(HL)6(H2O)8](I)·8H2O (6) crystallizes as a three-dimensional (3D) framework. Although these assemblies adopt different topologies, the {4(2).6} linear motif found in 1 is discernible in the structures of 2, 5, and 6, in which the higher dimensionality arises from further bridging of these subunits by uranyl (2), copper (5), or both uranyl and dysprosium (6) cations. The tetracarboxylic/ate ligands have their two aromatic rings nearly perpendicular to one another. No two of them adopt the same coordination mode in this series (except in the similar complexes 3 and 4), but chelation involving one carboxylate group from each ring is nearly ubiquitous, and the ensuing position of the cation favors the formation of planar architectures. The emission spectra of complexes 2-5 measured in the solid state show the usual uranyl vibronic fine structure, although with significant differences in the emission intensity, while complete quenching of the luminescence is observed in 1.

Uranyl and uranyl-3d block cation complexes with 1,3-adamantanedicarboxylate: crystal structures, luminescence, and magnetic properties.

The reaction of 1,3-adamantanedicarboxylic acid (LH2) with uranyl nitrate under solvo-hydrothermal conditions, either alone or in the presence of additional metal cations (Co(2+), Ni(2+), or Cu(2+)) gives a series of nine complexes displaying a wide range of architectures. While [UO2(L)(H2O)]·1.25CH3CN (1) and [UO2(L)(DMF)] (2) are one-dimensional (1D) species analogous to that previously known, [H2NMe2]2[(UO2)2(L)3]·1.5H2O (3), which includes dimethylammonium counterions generated in situ, is a three-dimensional (3D) framework, and [UO2(L)(NMP)] (4) (NMP = N-methyl-2-pyrrolidone) is a braid-shaped 1D polymer. When 3d block metal ions are present and bound to 2,2'-bipyridine (bipy) coligands, their role is reduced to that of decorating species attached to uranyl-containing 1D polymers, as in [UO2M(L)2(bipy)2]·0.5H2O with M = Co (5) or Ni (6), and [(UO2)2Cu2(L)3(NO3)2(bipy)2]·0.5H2O (9), or of counterions, as in [Ni(bipy)3][(UO2)4(O)2(L)3]·3H2O (7), in which a two-dimensional (2D) assembly is built from tetranuclear uranyl-containing building units. In contrast, the heterometallic 3D framework [UO2Cu(L)2] (8) can be isolated in the absence of bipy. The emission spectra measured in the solid state display the usual uranyl vibronic fine structure, with various degrees of resolution and quenching, except for that of complex 7, which shows emission from the nickel(II) centers. The magnetic properties of complexes 5, 6, 8, and 9 were investigated, showing, in particular, the presence of zero-field splitting effects in 6 and weak antiferromagnetic interactions in 9.