Structural, spectroscopic and passivation properties of a novel binuclear clamshell-type zinc(II) phthalocyanine as gate dielectric for OFET

WOS: 000427932100008A novel clamshell-type binuclear zinc(II) phthalocyanine (2) was synthesized by cross condensation of the bisphthalonitrile (1) with 4-tert-butylphthalonitrile and zinc acetate in 1:10:4 ratio. The structure of the novel compound was characterized by elemental analysis, UV-vis, FT-IR (ATR), HR MALDI-TOF mass, H-1 NMR, C-13 DEPT NMR and H-1-H-1 COSY NMR methods. Applying electronic absorption spectroscopy and density functional theory (DFT) revealed that in THF the geometry of 2 is twisted to adopt an intermediate clamshell conformation in which the spacing between the Zn centers is about 8.1 angstrom, providing a very good account of the observed spectrum exhibiting the characteristic B (Soret) band at 347 nm and the Q band at 673 nm. In solution, 2 was found to exist in non-aggregated form. The calculated fluorescence quantum yields (Phi(F) = 0.23 in THF and 0.10 in DMF) were relatively reduced in comparison to that of std ZnPc. In particular, understanding of leakage current conduction mechanisms in gate dielectrics is crucial for the development of field effect transistors with improved device performance. Analysis of the reverse bias current-voltage data indicated that the origin of leakage current conduction mechanisms in clamshell-type zinc(II) phthalocyanine is Poole-Frenkel emission. The capacitance density of 12.7 nF cm(-2) at 5 Hz. and 12.1 nF cm(-2) at 13 MHz was obtained with the FTO/Pc/Au sandwich structure.Bulent Ecevit UniversityBulent Ecevit University [2015-72118496-05]The authors are grateful to the Bulent Ecevit University for financial support under the project [BAP Project No: 2015-72118496-05]. Some of the calculations were performed on Fencluster (Ege University, Faculty of Science) and TUBITAK-ULAKBIM Truba resources

Structural studies and cytotoxic activity of a new dinuclear coordination compound of palladium(II)-2,2:6,2-terpyridine with rigid dianionic 1,2,4-triazole-3-sulfonate linker

WOS: 000439744200011A new dinuclear coordination compound of palladium(II), [Pd-2(terpy)(2)(-tas-N-1,N-4)]SO(4)11H(2)O (1), was synthesized by tethering a doubly deprotonated 1,2,4-triazole-3-sulfonate (tas) linker generated in situ via oxidation of 1,2,4-triazole-3-thione (tat) under the synthetic conditions. X-ray diffraction analysis reveals that tat molecules adopt the thione form in the solid state, and are combined in infinite chains by symmetrically related classical intermolecular hydrogen bonds N1H1S1, N3H3N2 to give rise to R-2(2)(7) pattern in one-dimensional chains along the b-axis propagating along the a-axis. Further short contacts through lone pairs of N2S1 on the rings between the adjacent chains along the a-axis lead to a two-dimensional network structure. Compound 1 was characterized using infrared, H-1 NMR and UV-visible spectroscopies, electrospray ionization mass spectrometry and X-ray crystallography. The crystal structure determination of 1 reveals that the Pd(II) ions are coordinated with four nitrogen atoms: three from terpy and one from tas acting as an end-to-end (-1,4) bridging ligand. The Pd(II) ions in 1 adopt a distorted square planar geometry. The anti-growth effect of 1 was tested on colorectal cancer (HCT-15), non-small-cell lung cancer (A549), prostate cancer (PC-3) and cervical cancer (HeLa) cell lines using sulforhodamine B viability assay. The cytotoxic effect was further confirmed using adenosine triphosphate viability assay. Compound 1 shows a promising cytotoxic activity in the diverse cancer cell models in vitro (p <0.0001).Turkish Scientific and Technical Research Council (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [214Z090]Turkish Scientific and Technical Research Council (TUBITAK), Grant/Award Number: 214Z09

Electrochemical and photovoltaic studies on water soluble triads: Metallosupramolecular self-assembly of ditopic bis(imidazole) perylene diimide with platinum(II)-, and palladium(II)-2,2 ':6 ',2 ''-terpyridyl complex ions

WOS: 0004043099000221,6,7,12-tetrakis-(4-methoxyphenoxy)perylene-3,4,9,10-tetracarboxylic dianhydride was functionalized to possess imidazole ligating sites at the imide positions, namely N,N'-bis(3-propylimidazole)-1,6,7,12-tetrakis-(4-methoxyphenoxy)perylene diimide (PDI-1). By using metal ion-ligand coordination approach, self-assembly of newly synthesized ditopic ligand (PDI-1) with 2,2':6',2"-terpyridyl-platinum(II) and/or-palladium(II) complex ions produced novel water soluble triads [(terpy)M(II)-(PDI-1)-M(II)(terpy)](NO3)(4), M(II) = Pt(II) (PDI-2), and Pd(II) (PDI-3), respectively. The isolated triads were characterized by FT-IR, 1D-NMR (H-1 NMR and C-13 DEPT NMR), 2D-NMR (H-1-H-1 COSY, H-1-C-13 HSQC, H-1-C-13 HMBC), MALDI TOF mass.and UV/Vis spectroscopy. Redox and electrochromic properties of the compounds have been identified by electrochemical, in situ spectroelectrochemical, and in situ electrocalorimetric measurements. The measurements showed that the novel chromophores display both a reduction and oxidation process, with considerably narrow electrochemical HOMO-LUMO band gaps in suitable solvents. The reduction of the novel compounds at modest potentials especially, makes these novel chromophores good electron acceptors. Net spectral changes between the blue, red or pink and green colours suggested that the novel compounds are suitable for application in electrochromic devices. Furthermore, the introduction of the square-planar Pt(II) and/or Pd(II)-terpyridyl units to the PDI core by 'coordination to the imidazole ends of the PDI moiety strongly influenced the performance of the photovoltaic devices. (C) 2017 Elsevier Ltd. All rights reserved.Turkish Scientific and Technical Research Council under the grant [TUBITAK] [214Z090]; Bulent Ecevit University [BAP Project] [2015-72118496-05]; Turkish Academy of Sciences (TUBA)Turkish Academy of SciencesThe authors are grateful to the Turkish Scientific and Technical Research Council for support of this project under the grant [TUBITAK-Project No: 214Z090]. We also gratefully thank to Bulent Ecevit University for partial financial support under the project [BAP Project No: 2015-72118496-05]. Authors also thank Turkish Academy of Sciences (TUBA) for financial support

Electrochemical, photovoltaic and DFT studies on hybrid materials based on supramolecular self-assembly of a ditopic twisted perylene diimide with square-planar platinum(II)- and/or palladium(II)-2,2 ':6 ',2 ''-terpyridyl complex ions

WOS: 000449241200008A ditopic bridging ligand, N,N'-bis(pyridine)-1,6,7,12-tetrakis-(4-methoxyphenoxy)perylene diimide (1) was synthesized. Metallosupramolecular self-assembly of 1 with 2,2':6',2 ''-terpyridyl-platinum(II) and/or -palladium (II) complex ions afforded to new triads [(terpy)M(II)-(1)-M(II)(terpy)1(NO3)(4) where, M(II) = Pt(II) (2), and Pd (II) (3), respectively. These isolated triads 2 and 3 and also free ligand 1 were fully characterized by FT-IR, H-1 NMR, C-13 DEPT NMR, H-1-H-1 COSY NMR, MALDI TOF and HRMS (MALDI-TOF/TOF-MS) mass techniques and UV/Vis spectroscopy. DFT studies revealed that the molecular structure of 1 is highly distorted and deviated from the planarity by bulky methoxyphenyl groups at bay positions. The calculated HOMO and LUMO are located on the PDI core and phenyl groups, and the band gap was found to be 2.27, 2.23 and 2.24 eV in DMSO for 1, 2 and 3, respectively. The calculated UV/Vis spectra are in good agreement with those of experimental results. Electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric measurements in solution suggested that redox processes of the compounds are accompanied by favourable electron transport properties with remarkably narrow HOMO-LUMO gaps and intense light absorption over the visible range. The association of usually reversible and fast electron transfer processes with the net colour changes in solution pointed out the applicability of the compounds as an electrochromic material. The electrochromic performance measurements with the films of the compounds on indium tin oxide glass provided additional support for their usability as a colour changing material in electrochromic devices. Surface morphologies of the films were characterized by scanning electron microscopy (SEM). The metal complexes of 1, especially the platinum(II) complex (2), behaved as a good neutral and cathodic colouring electrochromic material with fast response time, long-term stability, and long-term write erase efficiency. The photovoltaic performance of the compounds as electron acceptor material was investigated by varying their relative ratio in the bulk heterojunction solar cells. It was found that the photovoltaic conversion efficiency of the devices strongly depends on the blend ratio. The optimized performance for the devices was obtained with the P3HT:PDIs (weight ratio 1.0:1.5) blended films. For this blend ratio, the device showed a maximum conversion efficiency of 3.91%, 8.17% and 5.18% for 1, 2 and 3, respectively. The results obtained reveal that employing 2 as an acceptor material has great potential for the development of highly efficient nonfullerene bulk heterojunction photovoltaic devices.Turkish Scientific and Technical Research CouncilTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [214Z090]; Turkish Academy of SciencesTurkish Academy of SciencesThe authors are grateful to the Turkish Scientific and Technical Research Council for support of this project under the grant [TUBITAK-Project No: 214Z090]. We also thank for computer time on FenCluster provided by Ege University Faculty of Science and TUBITAK-ULAKBIM Truba Resources. Ali Riza Ozkaya also thanks Turkish Academy of Sciences for partial support to this work. The authors gratefully thank Prof. Dr Bekir SALIH at the Hacettepe University for the MALDI-TOF and HRMS analysis

Electron/energy transfer studies on hybrid materials based on dinuclear coordination compounds of twisted perylene diimide

To understand the influence of transition metal ion coordination on the properties and performance of the triads, the symmetric bridging ligand, 1,10-phenanthroline-perylene diimide-1,10-phenanthroline, 1,10-Phen-PDI-1,10-Phen (1) comprising four electron-donating 4-methoxyphenoxy bulky groups at bay-positions and its corresponding square-planar coordination compounds with dichloroplatinum(II), [{PtCl2}(2)-1] (2) and palladium(II) [{PdCl2}(2)-1] (3) were prepared in order to tune the photochemical and optical properties of these hybrid materials. These triads show strong electronic absorption bands attributed to the PDI and M(II)(1,10-Phen)Cl-2 moieties in DMSO. UV-vis absorption spectra of the compounds were calculated using Time-Dependent Density Functional Theory (TDDFT) for the ground state optimized structures in DCM. Current results indicate that 2 has the lowest HOMO-LUMO gap (2.29 eV in DCM) among the investigated molecules. The energy and charge transfer processes with tailoring molecular structures are one of the important strategies for the design of future functional triads based on donor and acceptor moieties for hybrids optoelectronic devices. Thus, we studied linear absorption, fluorescence, and ultrafast transient absorption spectra measurements for the triads in DCM to investigate the impact of different functionalization strategies on the optical characteristics, photo-stability, and photo-induced charge-transfer (CT) processes. The observed ultrafast intramolecular charge transfer from donor units to acceptor part of 1-3 is related to fluorescence quenching and faster singlet state decay on transient absorption measurements. The intramolecular charge transfer mechanism was also compared with the unsymmetrical counterparts that were investigated previously. Symmetrical compounds exhibit faster charge transfer in comparison with the unsymmetrical compounds

Tetrahydroxyphthalocyanine as a potential nonlinear optical material

We have synthesized a new zinc(II)-phthalocyanine (ZnPc) incorporating hydroxyl groups at the pe-ripheral positions. This new zinc(II)-tetra-hydroxyphthalocyanine ( 1 ) has been characterized by high -resolution MALDI TOF MS, UV-Vis, FT-IR (ATR), and 1 H-and 13C-NMR techniques, and further by the electrochemical measurements. DFT and TD-DFT computations were performed to model plausible struc-ture and also analyze the electronic structure and optical properties of 1 . The effects of the polarity and hydrogen bonding ability of the hydroxyl substituents on the peripheral positions of 1 on the optical and electrochemical properties are reported in this study. The redox behavior of 1 in dimethyl sulfoxide (DMSO) was determined by voltammetry and colorimetry supported in situ spectroelectrochemistry. The nonlinear absorption and optical limiting (OL) properties of 1 were measured in tetrahydrofuran (THF) by utilizing the open aperture Z-scan technique with nanosecond pulses at 532 nm. The sample demon-strated good reverse saturable absorption and OL behaviors. The ultrafast pump-probe experiments re-vealed the intersystem crossing (ISC) mechanism (triplet-triplet transition) and the nonlinear absorption mechanism of the compound. The results indicate that this new phthalocyanine ( 1 ) can be considered a potential candidate for low-power OL applications.(c) 2022 Elsevier B.V. All rights reserved.Zonguldak Buelent Ecevit University [2015-72118496-05]; Turkish Academy of Sciences (TUBA)The authors thank Zonguldak Buelent Ecevit University for financial support under the project [BAP Project No: 2015-72118496-05 ]. Computer time on TUBITAK-ULAKBIM Truba resources are greatly acknowledged. Ali Riza OEzkaya and Bekir Salih also thank the Turkish Academy of Sciences (TUBA) for partial support to this study

A novel AB(3)-type trimeric zinc(II)-phthalocyanine as an electrochromic and optical limiting material

Acar-Selcuki, Nursel/0000-0001-9292-0637; Salih, Bekir/0000-0002-8542-6531; KARATAY, Ahmet/0000-0001-9373-801X; ISIK BUYUKEKSI, Sebile/0000-0002-6075-1725WOS: 000587715700019PubMed: 32959851Recent advances in the practical applications of metallophthalocyanines (MPcs) in different technological fields have stimulated us to design and synthesize a new asymmetric AB(3)-type trimeric zinc(II)-phthalocyanine (1). This bulky and high molecular weight compound was characterized by elemental analysis, H-1, C-13 DEPT, and H-1-H-1 NOESY NMR, HR MALDI-TOF mass spectrometry, UV-vis, and FT-IR (ATR) techniques. In-depth electrochemical studies show that 1 displays quasi-reversible three one-electron reductions and two one- or two-electron oxidation processes, rather than any redox processes including the transfer of three-electrons in one-step. Besides this, in situ spectroelectrochemical measurements suggest the good application potential of 1 as an electrochromic material in display technologies. A study of the nonlinear optical properties (NLOs) of 1 reveals that the poly(methylmethacrylate) (PMMA) composite film displays a much larger nonlinear absorption coefficient and a lower saturable absorption threshold for optical limiting when compared to the same Pc molecules in solution. Ultrafast transient absorption measurements reveal the intersystem crossing mechanism. Density functional theory (DFT) was used for the geometry optimizations and time dependent-DFT (TD-DFT) for HOMO/LUMO energies and electronic transitions for 1.Zonguldak Bulent Ecevit University [BAP Project]Bulent Ecevit University [2015-72118496-05]; Turkish Academy of Sciences (TUBA)Turkish Academy of SciencesThe authors are grateful to Zonguldak Bulent Ecevit University for financial support under the project [BAP Project No: 2015-72118496-05]. Some of the calculations were performed on Fencluster (Ege University, Faculty of Science) and TUBITAK-ULAKBIM Truba resources. Ali Riza Ozkaya and Bekir Salih also thank the Turkish Academy of Sciences (TUBA) for partial support for this work