Esra Altuntaş

Physicochemical Analysis of Ruthenium(II) Sensitizers of 1,2,3-Triazole-Derived Mesoionic Carbene and Cyclometalating Ligands

A series of heteroleptic bis(tridentate) ruthenium(II) complexes bearing ligands featuring 1,2,3-triazolide and 1,2,3-triazolylidene units are presented. The synthesis of the C^N^N-coordinated ruthenium(II) triazolide complex is achieved by direct C-H activation, which is enabled by the use of a 1,5-disubstituted triazole. By postcomplexation alkylation, the ruthenium(II) 1,2,3-triazolide complex can be converted to the corresponding 1,2,3-triazolylidene complex. Additionally, a ruthenium(II) complex featuring a C^N^C-coordinating bis(1,2,3-triazolylidene)pyridine ligand is prepared via transmetalation from a silver(I) triazolylidene precursor. The electronic consequences of the carbanion and mesoionic carbene donors are studied both experimentally and computationally. The presented complexes exhibit a broad absorption in the visible region as well as long lifetimes of the charge-separated excited state suggesting their application in photoredox catalysis and photovoltaics. Testing of the dyes in a conventional dye-sensitized solar cell (DSSC) generates, however, only modest power conversion efficiencies (PCEs).

Recent developments in the detailed characterization of polymers by multidimensional chromatography

Synthetic polymers as well as biopolymers reveal complex structures, such as variations in functionality, chain length and architecture. Therefore, combinations of different chromatographic techniques are a prerequisite for a detailed characterization. One possible approach is the combination of high performance liquid chromatography at critical conditions (LCCC) and size-exclusion chromatography, also named as two-dimensional chromatography, which allows the separation of the polymers according to different properties, like molar mass, chemical composition or functionality. In addition, LCCC hyphenated with different mass spectrometry techniques, e.g. MALDI-TOF or ESI-TOF, leads to additional information about molecular details of the polymeric structure. We summarize in this article the recent developments in two-dimensional chromatography of synthetic polymers and biopolymers since 2005.

Characterization of poly(2-oxazoline) homo- and copolymers by liquid chromatography at critical conditions.

In this study liquid chromatography at critical conditions for poly(2-ethyl-2-oxazoline)s (PEtOx) has been performed for the first time in order to analyze functional PEtOx homopolymers and block copolymers. Besides the verification of the critical point of adsorption with two series of ester end group functionalized PEtOx homopolymers, to evaluate the effect of both the chain length dependence and the end group polarity, using a cyano column with a solvent combination of 2-propanol and water, also two-dimensional liquid chromatography (2D-LC) has been applied for a poly(2-oxazoline) block copolymer. The combined characterization techniques provided further information about the polymerization procedure with regard to the formation of side-products by separation of the block copolymer from the corresponding homopolymer impurities. In addition, hyphenation of LCCC with MALDI-TOF MS and ESI-Q-TOF tandem mass spectrometry verified the obtained results.

Self-Assembly of 3,6-Bis(4-triazolyl)pyridazine Ligands with Copper(I) and Silver(I) Ions: Time-Dependant 2D-NOESY and Ultracentrifuge Measurements

Two 3,6-bis(R-1H-1,2,3-triazol-4-yl)pyridazines (R = mesityl, monodisperse (CH(2)-CH(2)O)(12)CH(3)) were synthesized by the copper(I)-catalyzed azide-alkyne cycloaddition and self-assembled with tetrakis(acetonitrile)copper(I) hexafluorophosphate and silver(I) hexafluoroantimonate in dichloromethane. The obtained copper(I) complexes were characterized in detail by time-dependent 1D [(1)H, (13)C] and 2D [(1)H-NOESY] NMR spectroscopy, elemental analysis, high-resolution ESI-TOF mass spectrometry, and analytical ultracentrifugation. The latter characterization methods, as well as the comparison to analog 3,6-di(2-pyridyl)pyridazine (dppn) systems and their corresponding copper(I) and silver(I) complexes indicated that the herein described 3,6-bis(1H-1,2,3-triazol-4-yl)pyridazine ligands form [2×2] supramolecular grids. However, in the case of the 3,6-bis(1-mesityl-1H-1,2,3-triazol-4-yl)pyridazine ligand, the resultant red-colored copper(I) complex turned out to be metastable in an acetone solution. This behavior in solution was studied by NMR spectroscopy, and it led to the conclusion that the copper(I) complex transforms irreversibly into at least one different metal complex species.

Tandem mass spectrometry of poly(ethylene imine)s by electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)

In this contribution, linear poly(ethylene imine) (PEI) polymers, which are of importance in gene delivery, are investigated in detail by using electrospray ionization-quadrupole-time of flight (ESI-Q-TOF) and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS). The analyzed PEIs with different end groups were synthesized using the polymerization of substituted 2-oxazoline via a living cationic ring-opening polymerization (CROP) and a subsequent hydrolysis under acidic conditions. The main goal of this study was to identify linear PEI polymers in a detailed way to gain information about their fragmentation pathways. For this purpose, a detailed characterization of three different linear PEIs was performed by using ESI-Q-TOF and MALDI-TOF MS in combination with collision-induced dissociation (CID) experiments. In ESI-MS as well as MALDI-MS analysis, the obtained spectra of PEIs resulted in fitting mass distributions for the investigated PEIs. In the tandem MS analysis, a 1,2-hydride shift with a charge-remote rearrangement via a four-membered cyclic transition state, as well as charge-induced fragmentation reactions, was proposed as the main fragmentation mechanisms according to the obtained fragmentation products from the protonated parent peaks. In addition, heterolytic and homolytic cleavages were proposed as alternative fragmentation pathways. Moreover, a 1,4-hydrogen elimination was proposed to explain different fragmentation products obtained from the sodiated parent peaks.

Incorporation of Polymerizable Osmium(II) Bis-terpyridine Complexes into PMMA Backbones

For the first time, an Os(II) bis-terpyridine complex bearing a polymerizable methacryloyl function was synthesized and subsequently copolymerized with MMA using the RAFT polymerization technique. The well-defined polymer was analyzed by SEC, ESI-TOF MS, 1H NMR spectroscopy as well as UV–Vis absorption and emission spectroscopy. The lifetime as well as redox potentials of the complex and the corresponding polymer were also determined. Additionally, the film forming properties of the polymer were investigated and preliminary UV–Vis absorption as well as emission experiments were carried out with a second donor pendant polymer revealing energy transfer from the donor to the Os(II) complex.Graphical AbstractThe synthesis and subsequent polymerization of a methacrylate functionalized Os(II) bis-terpyridine complex is described. The copolymerization with MMA resulted in a polymer that features the well-defined optical and electrochemical properties of the complex combined with typical polymer properties.

Determination of the relative ligand-binding strengths in heteroleptic IrIII complexes by ESI-Q-TOF tandem mass spectrometry

An electrospray ionization quadrupole time-of-flight mass spectrometer has been utilized to investigate the relative ligand-binding strengths in a series of heteroleptic-charged iridium(III) complexes of the general formula [(C^N)(2) Ir(III) (S-tpy)](PF(6) ) by using variable collision energies. Collision-induced dissociation experiments were performed in order to study the stability of the Ir(III) complexes that are, for instance, suitable phosphors in light-emitting electrochemical cells. The ratio of signal intensities belonging to the fragment and the undissociated complex depends on the collision energy applied for the tandem mass spectra (MS/MS) analysis. By defining the threshold collision energy and the point of complete complex dissociation, it is possible to estimate the relative complex stabilities depending on the nature of the coordinated ligands [i.e. type of cyclometalating ligand (C^N), substituents on the S-shaped terpyridine (S-tpy)]. The collision energy values differed as a function of the coordination sphere of the Ir(III) centers.

Detailed characterization of poly(2‐ethyl‐2oxazoline)s by energy variable collision‐induced dissociation study

RATIONALE Poly(2-oxazoline)s are important polymers and can be considered as pseudo-peptides which makes them important for biomedical and life science applications. This prompts the need for a detailed characterization of these polymers via different analytical tools such as mass spectrometry. Here, the energy-variable collision-induced dissociation (CID) of poly(2-ethyl-2-oxazoline)s was studied by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOFMS/MS) to gain further structural information about this polymer type. METHODS All polymers were analyzed using manual flow injection of samples into an ESI-QTOF mass spectrometer. Mass spectra (MS and MS/MS) were obtained in the positive ion mode over a mass-to-charge (m/z) range from 50 to 3000. RESULTS The dependency of the fragmentation patterns as a function of collision energy was examined and the characteristic collision energy (CCE or CE50 ) values for various poly(2-ethyl-2-oxazoline)s with different end-groups were calculated. The effect of molar masses on the CCE values was investigated via the survival yield (SY) method and a linear relationship between CCE values and the degree of polymerization for the PEtOx polymers was observed. CONCLUSIONS This study showed that ESI-MS/MS is very useful for differentiating poly(2-ethyl-2-oxazoline)s with different end-groups by varying the collision energy. The SY method has the potential to determine the importance of the end-groups on the fragmentation behavior of this polymer type.