Your browser doesn't support javascript.
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 142
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Chemistry ; 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32520425

RESUMO

The synthesis of linear symmetric ethynyl- and acetylide- amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [Me3SiC≡CC(NDipp)2}M2] (Dipp = 2,6-diisopropylphenyl) (M = Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n-butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh3)AuC≡CC(NDipp)2}2M2] (M = Cu, Au). The corresponding Ag complex [{(PPh3)AuC≡CC(NDipp)2}2Ag2] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue-green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20 - 295 K. Emission quantum yields of up to 41% at room temperature were determined. Furthermore, similar emissions with quantum yields of 15% were observed for the two most brightly luminescent complexes in thf solution.

2.
J Phys Chem Lett ; 11(7): 2675-2681, 2020 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-32167769

RESUMO

The photophysics of the isolated trianion Ag29(BDT)123- (BDT = benzenedithiolate), a ligand-protected cluster comprising BDT-based ligands, terminating a shell of silver thiolates and a core of silver atoms, was studied in the gas phase by femtosecond time-resolved, pump-probe photoelectron spectroscopy. UV excitation at 490 nm populates one or more singlet excited states with significant charge transfer (CT) character in which electron density is shifted from shell to core. These CT states relax on an average time scale of several hundred femtoseconds by charge recombination to yield either the vibrationally excited singlet ground state (internal conversion) or a long-lived triplet (intersystem crossing). Our study is the first ultrafast spectroscopic probe of a ligand-protected coinage metal cluster in isolation. In the future, it will be interesting to study how cluster size, overall charge state, or heteroatom doping can be used to tune the corresponding relaxation dynamics in the absence of solvent.

3.
ACS Nano ; 2020 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-31920075

RESUMO

Single-walled carbon nanotubes as emerging quantum-light sources may fill a technological gap in silicon photonics due to their potential use as near-infrared, electrically driven, classical or nonclassical emitters. Unlike in photoluminescence, where nanotubes are excited with light, electrical excitation of single tubes is challenging and heavily influenced by device fabrication, architecture, and biasing conditions. Here we present electroluminescence spectroscopy data of ultra-short-channel devices made from (9,8) carbon nanotubes emitting in the telecom band. Emissions are stable under current biasing, and no enhanced suppression is observed down to 10 nm gap size. Low-temperature electroluminescence spectroscopy data also reported exhibit cold emission and line widths down to 2 meV at 4 K. Electroluminescence excitation maps give evidence that carrier recombination is the mechanism for light generation in short channels. Excitonic and trionic emissions can be switched on and off by gate voltage, and corresponding emission efficiency maps were compiled. Insights are gained into the influence of acoustic phonons on the line width, absence of intensity saturation and exciton-exciton annihilation, environmental effects such as dielectric screening and strain on the emission wavelength, and conditions to suppress hysteresis and establish optimum operation conditions.

4.
Dalton Trans ; 48(48): 17704-17708, 2019 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-31768515

RESUMO

We report the synthesis and catalytic application of a highly stable distance-defined Au/Ru heterobimetallic complex. [2.2]Paracyclophane serves as a backbone, holding the two metal centers in a spatial orientation and metal-metal fixed distance. The Au/Ru heterobimetallic complex is highly stable, easily accessible and exhibits promising catalytic activity in a visible-light mediated dual Au/Ru Meyer-Schuster rearrangement.

5.
Phys Chem Chem Phys ; 21(35): 18877-18892, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31436767

RESUMO

We present high-resolution trapped ion mobility spectrometry (TIMS) measurements for fullerene ions in molecular nitrogen. Three different charge states were studied (monocations, monoanions and dianions) with fullerenes ranging in size from C60 to C150. Ions were prepared by either electrospray ionization (ESI, for mono- and dianions) or by atmospheric pressure chemical ionization (APCI, for monocations) of a preformed fullerene soot extract solution. We demonstrate that TIMS allows to identify (and separate) constituent isomers in favorable cases. Using DFT calculations based on known condensed phase structures and trajectory method (TM) calculations we can reproduce the experimental TIMSCCSN2 for fullerenes up to C108 to within 0.5%. Using candidate structures based on quantum chemical predictions, we have also obtained structural information for fullerenes C110-C150- a size range not previously accessed in condensed phase studies. We find that soluble fullerenes in this size have near-spherical rather than tubular structures. While the TM programs presently available for CCS modelling do a remarkably good job at describing the ion mobility of high (and even giant) fullerenes we observe a slight but systematic size-dependent deviation between TIMSCCSN2 values and our best computational fits which may reflect systematic bonding changes as the cage size increases.

6.
J Am Soc Mass Spectrom ; 30(10): 1973-1980, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31240563

RESUMO

We have used trapped ion mobility spectrometry (TIMS) to obtain highly accurate experimental collision cross sections (CCS) for the fullerene C80- and the endohedral metallofullerenes La2@C80-, Sc3N@C80-, and Er3N@C80- in molecular nitrogen. The CCS values of the endohedral fullerenes are 0.2% larger than that of the empty cage. Using a combination of density functional theory and trajectory calculations, we were able to reproduce these experimental findings theoretically. Two effects are discussed that contribute to the CCS differences: (i) a small increase in fullerene cage size upon endohedral doping and (ii) charge transfer from the encapsulated moieties to the cage thus increasing the attractive charge-induced dipole interaction between the (endohedral) fullerene ion and the nitrogen bath gas molecules.

7.
Chem Sci ; 10(18): 4742-4749, 2019 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-31160950

RESUMO

The enantiomerically pure ligand P,P-diphenyl-N,N'-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M2{(R)-PEPIA}2] (M = Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs2{(R)-PEPIA}2] (6d ) and 1D-polymeric ([Cs{(R)-PEPIA}] n ) (6p ) species in a 1 : 1 ratio. The coordination polymer 6p features a unique sinus-shaped configuration of repeating -Cs-N-P-N-Cs-N-P-N- units. Unusual photoluminescence (PL) properties were found for solid 1-6: in contrast to the fluorescent ligand 1, the alkali metal complexes show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above ∼150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. DFT calculations support that both 1 and 2-6d have similar singlet and triplet excited states with energy separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore dimerization may serve as a tool to effect ISC for the design of TADF emitters.

8.
J Phys Chem A ; 123(25): 5325-5333, 2019 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-31150229

RESUMO

A series of cationic molecular fragments (C n+, n = 11, 12, 15, 16, 18, and 21), produced by electron-impact ionization of C60 in the gas phase, were each mass-selected and accumulated in cryogenic Ne matrices. Optical absorption measurements in the UV-vis and IR spectral ranges reveal linear carbon chain structures. In particular, we have observed the known electronic transitions of linear C11, C15, and C21. The NIR transitions of linear C15-, C16-, and C18- have also been detected, indicating that soft-landing of the corresponding cations can also involve charge-changing. Newly observed electronic absorptions at 410.3 and 429.9 nm have been assigned to linear C18 absorptions at 438.2, 443.5, 422.3, and 433.7 nm, to linear C15+, and absorption at 395.5 nm, to linear C16. Increasing deposition energy leads to fragmentation upon impact. This is indicated by absorptions of C10 (313, 316.3 nm), when depositing C n+ ( n = 11, 15, 16) as well as C12 (332 nm) or C14 (347.4, 356.6 nm), when depositing C15+ or C16+, respectively. These were previously assigned to cyclic isomers. We reassign them to linear isomers here on the basis of plausibility arguments. The observations have been supported by time-dependent density functional theory calculations for ring and chain isomers of C n+/-/0, 10 ≤ n ≤ 20 up to the vacuum-UV range. The electronic absorptions of carbon chains are at least 1 order of magnitude stronger than all NIR electronic absorptions of C60+, which have recently been attributed to several of the diffuse interstellar bands. Considering that fullerene multifragmentation yields long carbon chains that have very strong absorptions both in the UV-vis and IR spectral regions, these systems appear to be good candidates to be observed in regions of space containing fullerenes.

10.
Dalton Trans ; 48(41): 15427-15434, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31086882

RESUMO

A series of homo- and hetero-polynuclear coinage metal complexes based on a phosphine-substituted 1,2,3-triazole system is presented. Besides the P,N-ligand 1-benzyl-4-(diphenylphosphanyl)-1H-1,2,3-triazole (LPN), the P,C-donor ligand 1-benzyl-4-(diphenylphosphanyl)-3-methyl-1H-1,2,3-triazolium (LPCH+), featuring a potential mesoionic carbene moiety, was obtained by methylation of LPN. Starting from the monogold chloride complexes AuCl(LPN/LPC), the syntheses of a heterotrinuclear Au2Cu complex as well as a digold carbene complex are described. The multinuclear complexes show metallophilic interactions. Their photophysical properties were investigated by temperature-dependent photoluminescence (PL) measurements. In particular, the digold complex shows interesting PL properties including narrow exciton peaks arising in the excitation and emission spectra below 50 K. These might be related to the molecular 'chains' in the crystal structure of the digold complex, formed by phenyl ligand stacking.

11.
Langmuir ; 35(10): 3790-3796, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30758209

RESUMO

The length of a carbon nanotube is an important dimension that has to be adjusted to the requirements of an experiment or application, e.g., through sorting methods. So far, atomic force microscopy (AFM) has been the method of choice for measuring length distributions, despite being an ex situ method with apparent shortcomings. In this work, we explore analytical ultracentrifugation (AUC) as an in situ method for measuring the length distribution of polymer-wrapped (7, 5) single-walled carbon nanotubes dispersed in toluene. This is an AUC study of nanotubes in nonaqueous media, the preferred media for nanotubes used in device fabrication. In AUC, the temporally and spatially dependent change in optical absorption of a sample is measured under centrifugation. The resulting sedimentation curves can be deconvoluted with a standard data processing procedure (SEDFIT), to yield the sedimentation coefficient distribution. However, the conversion of the sedimentation coefficient distribution into a length distribution is nontrivial and requires finding a suitable model for the nanotube friction coefficient. Also, since AUC is based on optical absorption, it yields a volume distribution and not a number distribution as obtained from AFM reference data. By meeting these challenges and finding a surprisingly simple empirical flexible-chain-like model to describe the sedimentation behavior of one specific chiral structure, we suggest AUC as a viable method for measuring in situ nanotube length distributions of nonaqueous dispersions.

12.
Chemistry ; 25(15): 3799-3808, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30664818

RESUMO

Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize AuI -TlI metallopolymers, displaying novel and unusual structural motifs of the metal-metal backbones in the solid state: a discrete molecular cluster, 1D chains of interconnected dimers, tetramers, or dodecamers of Au-Tl units, and a 2D-plane network, consisting of alternating edge-linked (AuTl)6 and (AuTl)4 cycles. The formation of the different architectures was primarily controlled by the steric demand of the acetylide-substituent groups. Thus, the bulkiest 2,6-diisopropylphenyl derivative yielded a molecular cluster [Tl2 Au3 ]. Most compounds showed bright visible photoluminescence with quantum yields of up to 25 % at ambient temperature. The color of the emitted light significantly differs with the network structure. Furthermore, theoretical studies of singlet excitations in the molecular cluster, as well as NMR and mass-spectrometric investigations of the fragmentation of the metallopolymers in solution are described in detail.

13.
J Chem Phys ; 149(19): 194701, 2018 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-30466281

RESUMO

Temperature Programmed Desorption (TPD) spectroscopy was used to determine the binding energies of polycyclic aromatic hydrocarbons C n H m (22 ≤ n ≤ 60) with highly oriented pyrolytic graphite. These energies were then used to estimate the dispersive graphite interlayer cohesion by means of a refined extrapolation method proposed by Björk et al. This yields a cohesion energy of 44.0 ± 3.8 meV per carbon atom. We discuss some limits of the TPD-based approach and contrast our values with previous determinations of the interlayer cohesion energy of graphite.

14.
Chemphyschem ; 19(22): 3050-3060, 2018 11 19.
Artigo em Inglês | MEDLINE | ID: mdl-30204284

RESUMO

Lanthanide ions (DyIII , EuIII ) are stabilized by coordination with two Schiff base ligands in compounds [Dy{H3 L}2 ](NO3 )(EtOH)(H2 O)8 (1) and [Eu{H3 L}2 ](NO3 )(H2 O)8 (3) (H4 L, 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid). The latter is reported here for the first time. Both luminescence and ultrafast photodynamics after photoexcitation via a ligand absorption band (∼400 nm) have been studied. In solution, only the [Eu{H3 L}2 ]+ ([3]+ ) complex displays the typical lanthanide emission lines, whereas in gas phase both, [Dy{H3 L}2 ]+ ([1]+ ) and [3]+ , show their corresponding transitions depending on excitation energy. The ultrafast excited state dynamics, obtained in gas phase and in solution, are assigned to excited state intramolecular proton transfer processes in the ligands. The antenna ligand moiety of these complexes provides pockets for stabilization of two MnII ions so that we additionally investigated the photophysical behavior of the corresponding tri-nuclear (NHEt3 )2 [Ln{MnL}2 ](ClO4 )(H2 O)2 (Ln=DyIII , EuIII ) compounds (2, 4). Interestingly, the related complexes do not show lanthanide emission, neither in solution nor in gas phase. Transient data in solution and gas phase suggests an efficient quenching of the ligand's electronically excited state by strong interaction with the MnII ions. This effect could possibly be developed further into a design principle for luminescence-based sensing devices for metal cations.

15.
J Am Soc Mass Spectrom ; 29(7): 1431-1441, 2018 07.
Artigo em Inglês | MEDLINE | ID: mdl-29667165

RESUMO

We present gas-phase structures of dimers of MnIII and FeIII meso-tetra(4-sulfonatophenyl)porphyrin multianions with various amounts of sodium and hydrogen counterions. The structural assignments are achieved by combining mass spectrometry, ion mobility measurements, quantum chemical calculations, and trajectory method collision cross section calculations. For a common charge state, we observe significant topological variations in the dimer structures of [(MTPPS)2+nX](6-n)- (M=MnIII, FeIII; X=H, Na; n = 1-3) induced by replacing hydrogen counterions by sodium. For sodium, the dimer structures are much more compact, a finding that can be rationalized by the stronger interactions of the sodium cations with the anionic sulfonic acid groups of the porphyrins as compared to hydrogen. Graphical Abstract ᅟ.

16.
J Phys Chem A ; 122(17): 4357-4365, 2018 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-29630381

RESUMO

We performed a comprehensive gas-phase experimental and quantum-chemical study of the binding properties of molecular oxygen to iron and manganese porphyrin anions. Temperature-dependent ion-molecule reaction kinetics as probed in a Fourier-transform ion-cyclotron resonance mass spectrometer reveal that molecular oxygen is bound by, respectively, 40.8 ± 1.4 and 67.4 ± 2.2 kJ mol-1 to the FeII or MnII centers of isolated tetra(4-sulfonatophenyl)metalloporphyrin tetraanions. In contrast, FeIII and MnIII trianion homologues were found to be much less reactive-indicating an upper bound to their dioxygen binding energies of 34 kJ mol-1. We modeled the corresponding O2 adsorbates at the density functional theory and CASPT2 levels. These quantum-chemical calculations verified the stronger O2 binding on the FeII or MnII centers and suggested that O2 binds as a superoxide anion.

17.
J Phys Chem A ; 122(11): 2974-2982, 2018 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-29490134

RESUMO

We have used action photofragmentation spectroscopy in the visible spectral range (410 to 650 nm) to investigate the optical properties of different monomeric and dimeric M(II)-meso-tetra-(4-sulfonatophenyl)-porphyrin (with M = Pd(II), Cu(II), Zn(II)) multianions isolated in the gas phase without solvent. In particular, we report the position of the Q-bands (S0 → S1 transitions) as a function of charge state, counterions, oligomerization, and dimer structure type. The results for the monomers (charge states = 4- and 3-, sodiated and protonated) are in good agreement with TDDFT calculations and condensed-phase spectra. For both homo and heterometallic dimers, photofragmentation spectra were recorded for two charge states, 5- and 3-, corresponding to coplanar and cofacial structure types, respectively. The fragmentation patterns observed for the dimers depend significantly on charge state, with fragmentation into monomers being dominant for the 5- species, while the 3- charge state predominantly fragments by SO2 loss. The monomer → dimer Q-band spectral shifts observed in the gas phase were compared with the optical properties of porphyrin aggregates in solution.

18.
J Phys Chem A ; 122(9): 2461-2467, 2018 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-29451792

RESUMO

The gas-phase laser-induced photoluminescence of cationic mononuclear gadolinium and lutetium complexes involving two 9-oxophenalen-1-one ligands is reported. Performing measurements at a temperature of 83 K enables us to resolve vibronic transitions. Via comparison to Franck-Condon computations, the main vibrational contributions to the ligand-centered phosphorescence are determined to involve rocking, wagging, and stretching of the 9-oxophenalen-1-one-lanthanoid coordination in the low-energy range, intraligand bending, and stretching in the medium- to high-energy range, rocking of the carbonyl and methine groups, and C-H stretching beyond. Whereas Franck-Condon calculations based on density-functional harmonic frequency computations reproduce the main features of the vibrationally resolved emission spectra, the absolute transition energies as determined by density functional theory are off by several thousand wavenumbers. This discrepancy is found to remain at higher computational levels. The relative energy of the Gd(III) and Lu(III) emission bands is only reproduced at the coupled-cluster singles and doubles level and beyond.

19.
J Phys Chem Lett ; 9(4): 914-918, 2018 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-29406747

RESUMO

We present the cryo IR-PD spectra of the coadsorbed [Ru8(H2)1(N2)4]+ and [Ru8(N2)4(H2)1]+ species differing in the adsorption sequence of H2 and N2, which we record via application of tandem cryo ion trapping. We observe strong evidence for dissociative H2 adsorption, and the spectra reveal differences in the Ru-H stretching region, which we assign to distal and proximal hydrogen atom locations on the Ru8+ cluster, their migration likely hindered by preloaded nitrogen molecules and unaffected by subsequent N2 adsorption.

20.
Chemistry ; 24(23): 6094-6104, 2018 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-29377298

RESUMO

The hybrid ligand 3-(2,2'-bipyridine-6-ylmethyl)-1-mesityl-1H-imidazolylidene (NHCBipy ) featuring both carbene and N-donor sites, was selectively complexed with various d10 metal cations in order to examine its coordination behavior with regard to homo and heterometallic structures. Respective silver complexes can be obtained by the silver oxide route and are suitable transmetallation reagents for the synthesis of gold(I) compounds. Starting from the mononuclear complexes [(NHCBipy )AuCl], [(NHCBipy )Au(C6 F5 )] and [(NHCBipy )2 Au][ClO4 ], open-chain as well as cyclic heterobimetallic complexes containing Cu+ , Ag+ , Zn2+ , Cd2+ , and Hg2+ were synthesized. Furthermore, the homobimetallic species [(NHCBipy )2 M2 ][ClO4 ]2 (M=Cu, Ag) were obtained. All bimetallic compounds were fully characterized including single-crystal X-ray analysis. Their photoluminescence (PL) properties were investigated in the solid state at temperatures between 15 and 295 K and compared with those of the mononuclear species. There is a clear difference in PL properties between the open chain and the cyclic heterobimetallic complexes. The latter species show different PL properties, depending on the metals involved. In addition, collision-induced dissociation (CID) experiments were performed on electrosprayed cations of the cyclic heterobimetallic compounds, to compare the metal binding at the carbene and N-donor sites.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA