TY  - JOUR
A1  - Balischewski, Christian
A1  - Choi, Hyung-Seok
A1  - Behrens, Karsten
A1  - Beqiraj, Alkit
A1  - Körzdörfer, Thomas
A1  - Gessner, Andre
A1  - Wedel, Armin
A1  - Taubert, Andreas
T1  - Metal sulfide nanoparticle synthesis with ionic liquids state of the art and future perspectives
JF  - ChemistryOpen
N2  - Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nano-particle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.
KW  - Ionic liquids
KW  - ionic liquid crystals
KW  - ionic liquid precursors
KW  - metal
KW  - sulfides
KW  - catalysis
KW  - electrochemistry
KW  - energy materials
KW  - LED
KW  - solar
KW  - cells
Y1  - 2021
U6  - https://doi.org/10.1002/open.202000357
SN  - 2191-1363
VL  - 10
IS  - 2
SP  - 272
EP  - 295
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Kar, Manaswita
A1  - Körzdörfer, Thomas
T1  - Computational high throughput screening of inorganic cation based halide perovskites for perovskite only tandem solar cells
JF  - Materials Research Express
N2  - We search for homovalent alternatives for A, B, and X-ions in ABX(3) type inorganic halide perovskites suitable for tandem solar cell applications. We replace the conventional A-site organic cation CH3NH3, by 3 inorganic cations, Cs, K, and Rb, and the B site consists of metals; Cd, Hg, Ge, Pb, and Sn This work is built on our previous high throughput screening of hybrid perovskite materials (Kar et al 2018 J. Chem. Phys. 149, 214701). By performing a systematic screening study using Density Functional Theory (DFT) methods, we found 11 suitable candidates; 2 Cs-based, 3 K-based and 6 Rb-based that are suitable for tandem solar cell applications.
KW  - inorganic perovskites
KW  - tandem solar cells
KW  - density functional theory
Y1  - 2020
U6  - https://doi.org/10.1088/2053-1591/ab8c0d
SN  - 2053-1591
VL  - 7
IS  - 5
SP  - 1
EP  - 10
PB  - IOP Publ. Ltd.
CY  - Bristol
ER  - 
TY  - JOUR
A1  - Xiong, Tao
A1  - Włodarczyk, Radosław Stanisław
A1  - Gallandi, Lukas
A1  - Körzdörfer, Thomas
A1  - Saalfrank, Peter
T1  - Vibrationally resolved photoelectron spectra of lower diamondoids
BT  - a time-dependent approach
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry
N2  - Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ∼0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].
Y1  - 2018
U6  - https://doi.org/10.1063/1.5012131
SN  - 0021-9606
SN  - 1089-7690
VL  - 148
IS  - 4
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Abouserie, Ahed
A1  - Zehbe, Kerstin
A1  - Metzner, Philipp
A1  - Kelling, Alexandra
A1  - Günter, Christina
A1  - Schilde, Uwe
A1  - Strauch, Peter
A1  - Körzdörfer, Thomas
A1  - Taubert, Andreas
T1  - Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior
JF  - European journal of inorganic chemistry : a journal of ChemPubSoc Europe
N2  - Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
KW  - Ionic liquids
KW  - Alkylpyridinium salts
KW  - Structure elucidation
KW  - Phase transitions
Y1  - 2017
U6  - https://doi.org/10.1002/ejic.201700826
SN  - 1434-1948
SN  - 1099-0682
SP  - 5640
EP  - 5649
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Abouserie, Ahed
A1  - Zehbe, Kerstin
A1  - Metzner, Philipp
A1  - Kelling, Alexandra
A1  - Günter, Christina
A1  - Schilde, Uwe
A1  - Strauch, Peter
A1  - Körzdörfer, Thomas
A1  - Taubert, Andreas
T1  - Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior
JF  - European journal of inorganic chemistry : a journal of ChemPubSoc Europe
N2  - Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
KW  - Ionic liquids
KW  - Alkylpyridinium salts
KW  - Structure elucidation
KW  - Phase transitions
Y1  - 2017
U6  - https://doi.org/10.1002/ejic.201700826
SN  - 1434-1948
SN  - 1099-0682
SP  - 5640
EP  - 5649
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Knight, Joseph W.
A1  - Wang, Xiaopeng
A1  - Gallandi, Lukas
A1  - Dolgounitcheva, Olga
A1  - Ren, Xinguo
A1  - Ortiz, J. Vincent
A1  - Rinke, Patrick
A1  - Körzdörfer, Thomas
A1  - Marom, Noa
T1  - Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules III: A Benchmark of GW Methods
JF  - Journal of chemical theory and computation
N2  - The performance of different GW methods is assessed for a set of 24 organic acceptors. Errors are evaluated with respect to coupled cluster singles, doubles, and perturbative triples [CCSD(T)] reference data for the vertical ionization potentials (IPs) and electron affinities (EAs), extrapolated to the complete basis set limit. Additional comparisons are made to experimental data, where available. We consider fully self-consistent GW (scGW), partial self-consistency in the Green’s function (scGW0), non-self-consistent G0W0 based on several mean-field starting points, and a “beyond GW” second-order screened exchange (SOSEX) correction to G0W0. We also describe the implementation of the self-consistent Coulomb hole with screened exchange method (COHSEX), which serves as one of the mean-field starting points. The best performers overall are G0W0+SOSEX and G0W0 based on an IP-tuned long-range corrected hybrid functional with the former being more accurate for EAs and the latter for IPs. Both provide a balanced treatment of localized vs delocalized states and valence spectra in good agreement with photoemission spectroscopy (PES) experiments.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jctc.5b00871
SN  - 1549-9618
SN  - 1549-9626
VL  - 12
SP  - 615
EP  - 626
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Gallandi, Lukas
A1  - Marom, Noa
A1  - Rinke, Patrick
A1  - Körzdörfer, Thomas
T1  - Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules II: Non-Empirically Tuned Long-Range Corrected Hybrid Functionals
JF  - Journal of chemical theory and computation
N2  - The performance of non-empirically tuned long-range corrected hybrid functionals for the prediction of vertical ionization potentials (IPs) and electron affinities (EAs) is assessed for a set of 24 organic acceptor molecules. Basis set extrapolated coupled cluster singles, doubles, and perturbative triples [CCSD(T)] calculations serve as a reference for this study. Compared to standard exchange-correlation functionals, tuned long-range corrected hybrid functionals produce highly reliable results for vertical IPs and EAs, yielding mean absolute errors on par with computationally more demanding GW calculations. In particular, it is demonstrated that long-range corrected hybrid functionals serve as ideal starting points for non-self-consistent GW calculations.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jctc.5b00873
SN  - 1549-9618
SN  - 1549-9626
VL  - 12
SP  - 605
EP  - 614
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Bois, Juliana
A1  - Körzdörfer, Thomas
T1  - 0 How Bond Length Alternation and Thermal Disorder Affect the Optical
Excitation Energies of pi-Conjugated Chains: A Combined Density
Functional Theory and Molecular Dynamics Study
JF  - Journal of chemical theory and computation
N2  - We dissect the sources of error leading to inaccuracies in the description of the geometry and optical excitation energies of pi-conjugated polymers. While the ground-state bond length alternation is shown to be badly reproduced by standard functionals, the recently adapted functionals PBEh* and omega PBE* as well as the double hybrid functional XYGJ-OS manage to replicate results obtained at the CCSD(T) level. By analysis of the bond length alternation in the excited state, a sensitive dependence of the exciton localization on the long-range behavior of the functional and the amount of Hartree-Fock exchange present is shown. Introducing thermal disorder through molecular dynamics simulations allows the consideration of a range of thermally accessible configurations of each oligomer, including trans to cis rotations, which break the conjugation of the backbone. Thermal disorder has a considerable effect when combined with functionals that overestimate the delocalization of the excitation, such as B3LYP. For functionals with a larger amount of exact exchange such as our PBEh* and omega PBE*, however, the effect is small, as excitations are often localized enough to fit between twists in the chain.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jctc.5b01070
SN  - 1549-9618
SN  - 1549-9626
VL  - 12
SP  - 1872
EP  - 1882
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Sun, Haitao
A1  - Ryno, Sean
A1  - Zhong, Cheng
A1  - Ravva, Mahesh Kumar
A1  - Sun, Zhenrong
A1  - Körzdörfer, Thomas
A1  - Bredas, Jean-Luc
T1  - Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach
JF  - Journal of chemical theory and computation
N2  - We propose a new methodology for the first principles description of the electronic properties relevant for charge transport in organic molecular crystals. This methodology, which is based on the combination of a nonempirical, optimally tuned range separated hybrid functional with the polarizable continuum model, is applied to a series of eight representative molecular semiconductor crystals. We show that it provides ionization energies, electron affinities, and transport gaps in very good agreement with experimental values, as well as with the results of many-body perturbation theory-within the GW approximation at a fraction of the computational cost. Hence, this approach represents an easily applicable and computationally efficient tool to estimate the gas-to crystal phase shifts of the frontier-orbital quasiparticle energies in organic electronic materials.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jctc.6b00225
SN  - 1549-9618
SN  - 1549-9626
VL  - 12
SP  - 2906
EP  - 2916
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Megow, Jörg
A1  - Körzdörfer, Thomas
A1  - Renger, Thomas
A1  - Sparenberg, Mino
A1  - Blumstengel, Sylke
A1  - Henneberger, Fritz
A1  - May, Volkhard
T1  - Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction
JF  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Delta epsilon(m) is mainly caused by dispersion effects and depends sensitively on the molecules specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Delta epsilon(m)= -QW(m) in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while W-m is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI).
Y1  - 2015
U6  - https://doi.org/10.1021/acs.jpcc.5b01587
SN  - 1932-7447
VL  - 119
IS  - 10
SP  - 5747
EP  - 5751
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Gallandi, Lukas
A1  - Körzdörfer, Thomas
T1  - Long-Range Corrected DFT Meets GW: Vibrationally Resolved Photoelectron Spectra from First Principles
JF  - Journal of chemical theory and computation
N2  - We propose an entirely nonempirical and computationally efficient scheme to calculate highly reliable vibrationally resolved photoelectron spectra for molecules from first principles. To this end, we combine nonempirically tuned long-range corrected hybrid functionals with non-self-consistent many-body perturbation theory in the G(0)W(0) approximation and a Franck-Condon multimode analysis based on DFT-calculated frequencies. The vibrational analysis allows for a direct comparison of the GW-calculated spectra to gas-phase ultraviolet photoelectron measurements of neutral and anionic molecules, respectively. Direct comparison of the calculated peak maxima with experiment yields mean absolute errors below 0.1 eV for ionization potentials, electron affinities, and fundamental gaps, clearly outperforming commonly used G(0)W(0) approaches at similar numerical costs.
Y1  - 2015
U6  - https://doi.org/10.1021/acs.jctc.5b00820
SN  - 1549-9618
SN  - 1549-9626
VL  - 11
IS  - 11
SP  - 5391
EP  - 5400
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Sutton, Christopher
A1  - Körzdörfer, Thomas
A1  - Gray, Matthew T.
A1  - Brunsfeld, Max
A1  - Parrish, Robert M.
A1  - Sherrill, C. David
A1  - Sears, John S.
A1  - Bredas, Jean-Luc
T1  - Accurate description of torsion potentials in conjugated polymers using density functionals with reduced self-interaction error
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - We investigate the torsion potentials in two prototypical pi-conjugated polymers, polyacetylene and polydiacetylene, as a function of chain length using different flavors of density functional theory. Our study provides a quantitative analysis of the delocalization error in standard semilocal and hybrid density functionals and demonstrates how it can influence structural and thermodynamic properties. The delocalization error is quantified by evaluating the many-electron self-interaction error (MESIE) for fractional electron numbers, which allows us to establish a direct connection between the MESIE and the error in the torsion barriers. The use of non-empirically tuned long-range corrected hybrid functionals results in a very significant reduction of the MESIE and leads to an improved description of torsion barrier heights. In addition, we demonstrate how our analysis allows the determination of the effective conjugation length in polyacetylene and polydiacetylene chains.
Y1  - 2014
U6  - https://doi.org/10.1063/1.4863218
SN  - 0021-9606
SN  - 1089-7690
VL  - 140
IS  - 5
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Baier, Heiko
A1  - Metzner, Philipp
A1  - Körzdörfer, Thomas
A1  - Kelling, Alexandra
A1  - Holdt, Hans-Jürgen
T1  - Efficient palladium(II) precatalysts bearing 4,5-dicyanoimidazol-2-ylidene for the Mizoroki-Heck reaction
JF  - European journal of inorganic chemistry : a journal of ChemPubSoc Europe
N2  - The new N-heterocyclic carbene (NHC) complex [PdCl2{(CN)(2)IMes}(PPh3)] (2) ({(CN)(2)IMes}: 4,5-dicyano-1,3-dimesitylimidazol-2-ylidene) and the NHC palladacycle [PdCl(dmba){(CN)(2)IMes}] (3) (dmba: N,N-dimethylbenzylamine) have been synthesized by thermolysis of 4,5-dicyano-1,3-dimesityl-2-(pentafluorophenyl) imidazoline (1) in the presence of suitable palladium(II) precursors. The acyclic complex 2 was formed by ligand exchange using the mononuclear precursor [PdCl2(PPh3)(2)] and the palladacycle 3 was formed by cleavage of the dinuclear chloro-bridged precursor [Pd(mu-Cl)(dmba)](2). The new NHC precursor 1-benzyl-4,5-dicyano-2-(pentafluorophenyl)-3-picolylimidazoline (5) was formed by condensation of pentafluorobenzaldehyde with N-benzyl-N'-picolyldiaminomaleonitrile (4). The NHC palladacycle [PdCl2{(CN)(2)IBzPic}] (6) ({(CN)(2)IBzPic}: 1-benzyl-4,5-dicyano-3-picolylimidazol-2-ylidene) was prepared by in situ thermolysis of 5 in the presence of [PdCl2(PhCN)(2)]. The three palladium(II) complexes were characterized by NMR and IR spectroscopy, mass spectrometry and elemental analysis. In addition, the molecular structures of 2 and 3 were determined by X-ray diffraction. The pi-acidity of (CN)(2)IBzPic was compared with (CN)(2)IMes and perviously reported pi-acidic imidazol-2-ylidenes by NBO analysis. The Mizoroki-Heck (MH) reactions of various aryl halides with n-butyl acrylate were performed in the presence of complexes 2, 3 and 6. The new precatalysts showed high activity in the MH reactions giving good-to-excellent product yields with 0.1 mol-% pre-catalyst. The nature of the catalytically active species of 2, 3 and 6 was investigated by poisoning experiments with mercury and transmission electron microscopy. It was found that palladium nanoparticles formed from the precatalysts were involved in the catalytic process.
KW  - Homogeneous catalysis
KW  - Palladium
KW  - Cross coupling
KW  - Carbene ligands
Y1  - 2014
U6  - https://doi.org/10.1002/ejic.201402040
SN  - 1434-1948
SN  - 1099-0682
IS  - 18
SP  - 2952
EP  - 2960
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Marom, Noa
A1  - Körzdörfer, Thomas
A1  - Ren, Xinguo
A1  - Tkatchenko, Alexandre
A1  - Chelikowsky, James R.
T1  - Size effects in the interface level alignment of dye-Sensitized TiO2 clusters
JF  - The journal of physical chemistry letters
N2  - The efficiency of dye-sensitized solar cells (DSCs) depends critically on the electronic structure of the interfaces in the active region. We employ recently developed dispersion-inclusive density functional theory (DFT) and GW methods to study the electronic structure of TiO2 clusters sensitized with catechol molecules. We show that the energy level alignment at the dye-TiO2 interface is the result of an intricate interplay of quantum size effects and dynamic screening effects and that it may be manipulated by nanostructuring and functionalizing the TiO2. We demonstrate that the energy difference between the catechol LUMO and the TiO2 LUMO, which is associated with the injection loss in DSCs, may be reduced significantly by reducing the dimensions of nanostructured TiO2 and by functionalizing the TiO2 with wide-gap moieties, which contribute additional screening but do not interact strongly with the frontier orbitals of the TiO2 and the dye. Precise control of the electronic structure may be achieved via "interface engineering" in functional nanostructures.
Y1  - 2014
U6  - https://doi.org/10.1021/jz5008356
SN  - 1948-7185
VL  - 5
IS  - 14
SP  - 2395
EP  - 2401
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Keller, Adrian
A1  - Rackwitz, Jenny
A1  - Cauet, Emilie
A1  - Lievin, Jacques
A1  - Körzdörfer, Thomas
A1  - Rotaru, Alexandru
A1  - Gothelf, Kurt V.
A1  - Besenbacher, Flemming
A1  - Bald, Ilko
T1  - Sequence dependence of electron-induced DNA strand breakage revealed by DNA nanoarrays
JF  - Scientific reports
Y1  - 2014
U6  - https://doi.org/10.1038/srep07391
SN  - 2045-2322
VL  - 4
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Körzdörfer, Thomas
A1  - Parrish, Robert M.
A1  - Sears, John S.
A1  - Sherrill, C. David
A1  - Bredas, Jean-Luc
T1  - On the relationship between bond-length alternation and many-electron self-interaction error
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - Predicting accurate bond-length alternations (BLAs) in long conjugated molecular chains has been a major challenge for electronic-structure theory for many decades. While Hartree-Fock (HF) overestimates BLA significantly, second-order perturbation theory and commonly used density functional theory (DFT) approaches typically underestimate it. Here, we discuss how this failure is related to the many-electron self-interaction error (MSIE), which is inherent to both HF and DFT approaches. We use tuned long-range corrected hybrids to minimize the MSIE for a series of polyenes. The key result is that the minimization of the MSIE alone does not yield accurate BLAs. On the other hand, if the range-separation parameter is tuned to yield accurate BLAs, we obtain a significant MSIE that grows with chain length. Our findings demonstrate that reducing the MSIE is one but not the only important aspect necessary to obtain accurate BLAs from density functional theory.
Y1  - 2012
U6  - https://doi.org/10.1063/1.4752431
SN  - 0021-9606
VL  - 137
IS  - 12
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Ast, Sandra
A1  - Schwarze, Thomas
A1  - Müller, Holger
A1  - Sukhanov, Aleksey
A1  - Michaelis, Stefanie
A1  - Wegener, Joachim
A1  - Wolfbeis, Otto S.
A1  - Körzdörfer, Thomas
A1  - Dürkop, Axel
A1  - Holdt, Hans-Jürgen
T1  - A highly K+-Selective Phenylaza-[18]crown-6-Lariat-Ether-Based Fluoroionophore and its application in the sensing of K+ Ions with an optical sensor film and in cells
JF  - Chemistry - a European journal
N2  - Herein, we report the synthesis of two phenylaza-[18]crown-6 lariat ethers with a coumarin fluorophore (1 and 2) and we reveal that compound 1 is an excellent probe for K+ ions under simulated physiological conditions. The presence of a 2-methoxyethoxy lariat group at the ortho position of the anilino moiety is crucial to the substantially increased stability of compounds 1 and 2 over their lariat-free phenylaza-[18] crown-6 ether analogues. Probe 1 shows a high K+/Na+ selectivity and a 2.5-fold fluorescence enhancement was observed in the presence of 100 mm K+ ions. A fluorescent membrane sensor, which was prepared by incorporating probe 1 into a hydrogel, showed a fully reversible response, a response time of 150 s, and a signal change of 7.8% per 1 mm K+ within the range 1-10 mm K+. The membrane was easily fabricated (only a single sensing layer on a solid polyester support), yet no leaching was observed. Moreover, compound 1 rapidly permeated into cells, was cytocompatible, and was suitable for the fluorescent imaging of K+ ions on both the extracellular and intracellular levels.
KW  - crown compounds
KW  - fluorescence
KW  - gels
KW  - potassium
KW  - sensors
Y1  - 2013
U6  - https://doi.org/10.1002/chem.201302350
SN  - 0947-6539
SN  - 1521-3765
VL  - 19
IS  - 44
SP  - 14911
EP  - 14917
PB  - Wiley-VCH
CY  - Weinheim
ER  -