4.7 Article

Enlarging the π System of Phosphorescent (C∧C*) Cyclometalated Platinum(II) NHC Complexes

期刊

INORGANIC CHEMISTRY
卷 53, 期 12, 页码 6346-6356

出版社

AMER CHEMICAL SOC
DOI: 10.1021/ic500971z

关键词

-

资金

  1. BMBF [FKZ: 13N10477]

向作者/读者索取更多资源

Cyclometalated (C boolean AND C*) platinum(II) N-heterocyclic carbene (NHC) complexes are emerging as a new class of phosphorescent emitters for the application in organic light-emitting devices (OLEDs). We present the synthesis of six new complexes of this class to investigate the influence of extended pi systems. Therefore, six different NHC ligands with a varying number of additional phenyl substituents were used in combination with the monoanionic acetylacetonate (acac) ligand to obtain complexes of the general formula [(NHC)Pt-(II)(acac)].The complexes were fully characterized by standard techniques and advanced spectroscopic methods (Pt-195 NMR). For all complexes the solid-state structure determination revealed a square-planar coordination of the platinum atom. Absorption and emission spectra were measured in thin amorphous poly(methyl methacrylate) films at room temperature. Four compounds emit in the blue-green region of the visible spectrum with quantum yields of up to 81%.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

Article Chemistry, Multidisciplinary

C-C Cross-Couplings from a Cyclometalated Au(III) C∧N Complex: Mechanistic Insights and Synthetic Developments

Riccardo Bonsignore, Sophie R. Thomas, Mathilde Rigoulet, Christian Jandl, Alexander Poethig, Didier Bourissou, Giampaolo Barone, Angela Casini

Summary: The reactivity of gold complexes extends beyond pi-activation, showing promises for selective cross-couplings in various bond forming reactions. A gold-mediated C(sp(2))-C(sp) bond forming reaction was reported, and key intermediates were characterized using NMR, HR-ESI-MS, and crystallographic studies. DFT calculations provided insight into the structure and energetics, demonstrating rare examples of C(sp(2))-C(sp(2)) cross-couplings at Au(III).

CHEMISTRY-A EUROPEAN JOURNAL (2021)

Article Chemistry, Inorganic & Nuclear

Synthesis, Structural Characterization and Antiproliferative Activity of Gold(I) and Gold(III) Complexes Bearing Thioether-Functionalized N-Heterocyclic Carbenes

Riccardo De Marco, Marco Dal Grande, Marco Baron, Laura Orian, Claudia Graiff, Thierry Achard, Stephane Bellemin-Laponnaz, Alexander Pothig, Cristina Tubaro

Summary: A series of gold complexes with N-heterocyclic carbene ligands functionalized with a pendant thioether group were synthesized and characterized, showing moderate in vitro cytotoxicity towards breast cancer cells MCF7. The experimental aspects were rationalized through relativistic DFT calculations.

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (2021)

Article Biochemistry & Molecular Biology

Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Shengyang Guan, David C. Mayer, Christian Jandl, Sebastian J. Weishaeupl, Angela Casini, Alexander Poethig

Summary: A new solvatomorph of [Au-3(1-Methylimidazolate)(3)] has been identified and structurally characterized, showing dimer formation in the solid state driven by aurophilic interactions. Photophysical study combined with PXRD analysis revealed that all powder samples accessed from different preparation methods exhibit the same crystal structure. Strong thermochromism of the solid-state material was observed, ruling out a significant phase transition for the drastic change in emission properties.

MOLECULES (2021)

Article Chemistry, Inorganic & Nuclear

Bimetallic Platinum Group Complexes of a Macrocyclic Pyrazolate/NHC Hybrid Ligand

Thomas Pickl, Alexander Poethig

Summary: The study presents the synthesis, structural characterization, and photophysical properties of two new dinuclear PdII and Pt-II-NHC complexes. The d(8) metal ions are coordinated in a slightly distorted square-planar arrangement, exhibiting unique structural features and photoluminescence properties in both the solid state and in solution.

ORGANOMETALLICS (2021)

Article Chemistry, Multidisciplinary

New Access Routes to Privileged and Chiral Ligands for Transition-Metal Catalyzed Hydrogen Autotransfer (Borrowing Hydrogen), Dehydrogenative Condensation, and Alkene Isomerization Reactions

Sebastian Koller, Philippe Klein, Katja Reinhardt, Lukas Ochmann, Antonia Seitz, Christian Jandl, Alexander Poethig, Lukas Hintermann

Summary: A group of transition-metal catalyzed hydrogen moving reactions have been studied, with synthetic access routes established for a toolbox of structurally varied ligands and pincer complexes. Asymmetrically modified versions of established catalysts have been prepared for research towards asymmetric catalytic hydrogen moving reactions, showing potential in various model reactions such as transfer hydrogenation and alkene isomerization.

HELVETICA CHIMICA ACTA (2021)

Article Chemistry, Inorganic & Nuclear

Dimenthylphosphine P-Oxide as a Synthetic Platform for Bulky and Chiral Ligands with Dimenthylphosphino Donor Groups

Katja Reinhardt, Sebastian Koller, Philippe Klein, Corvin Lossin, Julia Gatzka, Philipp J. Altmann, Alexander Poethig, Lukas Hintermann

Summary: The study focuses on the attachment of di(1R)-menthylphosphino fragments to molecular scaffolds to create homochiral, bulky phosphine ligands for potential applications in coordination chemistry and transition-metal catalysis. Various transformations and reactions involving dimenthylphosphine P-oxide are explored, leading to the synthesis of new ligands and complexes with specific reactivity profiles due to the presence of menthyl groups. This approach shows promise for use in model palladium-catalyzed coupling reactions, with ligand 22 exhibiting high enantioselectivity in a specific biaryl-forming reaction.

ORGANOMETALLICS (2022)

Article Chemistry, Physical

Coordination Polymers Based on Carbazole-Derived Chromophore Linkers for Optimized Multiphoton Absorption: A Structural and Photophysical Study

Sebastian J. Weishaeupl, Yang Cui, Simon N. Deger, Hamad Syed, Aleksandr Ovsianikov, Juergen Hauer, Alexander Poethig, Roland A. Fischer

Summary: Multiphoton absorption (MPA) is of great interest in modern materials research, and metal-organic frameworks and coordination polymers (CPs) are potential materials to overcome the limitations of commonly used chromophore molecules. This article reports the synthesis and characterization of three new highly MPA-active CPs, and demonstrates their large two-photon absorption cross-sections, which are among the highest reported for CPs to date.

CHEMISTRY OF MATERIALS (2022)

Article Chemistry, Inorganic & Nuclear

Alkaline Earth Metal-Organic Frameworks Based on Tetratopic Anthraquinone-Based Linkers: Synthesis, Characterization, and Photochemical Applications

Joao Guilherme M. de Carvalho, Korbinian Geisser, Sebastian J. Weishaeupl, Roland A. Fischer, Alexander Poethig

Summary: A tetratopic bis(diphenylamino)anthraquinone linker is presented in this study. Its physicochemical and emissive properties are evaluated, and it successfully coordinates alkaline earth metals to form four new reported metal-organic frameworks (MOFs). The catalytic behavior of the ligand and the MOF materials towards the photooxidation of sulfides is also described.

INORGANIC CHEMISTRY (2022)

Article Chemistry, Medicinal

Exploring the Anticancer Activity of Tamoxifen-Based Metal Complexes Targeting Mitochondria

Valeria Scalcon, Riccardo Bonsignore, Jana Aupic, Sophie R. Thomas, Alessandra Folda, Alexandra A. Heidecker, Alexander Pothig, Alessandra Magistrato, Angela Casini, Maria Pia Rigobello

Summary: Two new hybrid metallodrugs of Au(III)(AuTAML)and Cu(II) (CuTAML) were designed to synergize the anticancer activity of both the metal centerand the organic ligand. These drugs showed antiproliferative effects against breast cancer cells and retained binding activity to estrogen receptor (ERα). Furthermore, they exhibited different reactivities and cytotoxic potencies, but displayed a capacity to induce mitochondrial damage.

JOURNAL OF MEDICINAL CHEMISTRY (2023)

Article Chemistry, Physical

Beyond Metal-Arenes: Monocarbonyl Ruthenium(II) Catalysts for Transfer Hydrogenation Reactions in Water and in Cells

Denise Lovison, Tobias Berghausen, Sophie R. Thomas, Jonathan Robson, Markus Drees, Christian Jandl, Alexander Poethig, Patrick Mollik, Dominik P. Halter, Walter Baratta, Angela Casini

Summary: In this study, water-soluble organometallic Ru(II) complexes were synthesized and found to act as anticancer agents by catalyzing transfer hydrogenation reactions with biomolecules. The structure-activity relationship and reaction mechanism were investigated, and the compounds were also tested for their anticancer activity in vitro.

ACS CATALYSIS (2023)

Article Multidisciplinary Sciences

Bright circularly polarized photoluminescence in chiral layered hybrid lead-halide perovskites

Shangpu Liu, Mikael Kepenekian, Stanislav Bodnar, Sascha Feldmann, Markus W. Heindl, Natalie Fehn, Jonathan Zerhoch, Andrii Shcherbakov, Alexander Poethig, Yang Li, Ulrich W. Paetzold, Aras Kartouzian, Ian D. Sharp, Claudine Katan, Jacky Even, Felix Deschler

Summary: This study reveals the unique photoluminescence properties of hybrid perovskite semiconductor materials, which can achieve high luminescence yields and circularly polarized photoluminescence at room temperature. The excellent photoluminescence performance is attributed to the suppression of nonradiative loss channels and the high rates of radiative recombination. These findings pave the way for high-performance solution-processed photonic systems and chiral-spintronic logic at room temperature.

SCIENCE ADVANCES (2023)

Review Materials Science, Multidisciplinary

Recent advances of multiphoton absorption in metal-organic frameworks

Sebastian J. Weishaeupl, David C. Mayer, Yang Cui, Pushpendra Kumar, Harald Oberhofer, Roland A. Fischer, Jurgen Hauer, Alexander Poethig

Summary: This review presents recent advances in metal-organic frameworks (MOFs) and coordination polymers (CPs) regarding their response properties to multiphoton absorption (MPA). It covers the theoretical background of MPA absorbing linker molecules, the effect of excitonic coupling within a rigid framework assembly, and compares different scanning and non-scanning measurement techniques for two-photon absorption (TPA) spectroscopy. Additionally, it comprehensively presents the latest progress of linker-based MPA materials and their relationship with framework structure and MPA cross section.

JOURNAL OF MATERIALS CHEMISTRY C (2022)

Article Chemistry, Inorganic & Nuclear

Highly-fluorescent BODIPY-functionalised metallacages as drug delivery systems: synthesis, characterisation and cellular accumulation studies

Brech Aikman, Riccardo Bonsignore, Ben Woods, Daniel Doellerer, Riccardo Scotti, Claudia Schmidt, Alexandra A. Heidecker, Alexander Poethig, Edward J. Sayers, Arwyn T. Jones, Angela Casini

Summary: Research focused on designing new metallosupramolecular structures for drug delivery. Two self-assembled metal cages capable of encapsulating anticancer drugs have been synthesized and characterized. The stability and intracellular localization of these structures have been confirmed, and their antiproliferative activity has been investigated.

DALTON TRANSACTIONS (2022)

Article Chemistry, Inorganic & Nuclear

Facile preparation of a cobalt diamine diketonate adduct as a potential vapor phase precursor for Co3O4films

Max Klotzsche, Davide Barreca, Lorenzo Bigiani, Roberta Seraglia, Alberto Gasparotto, Laura Vanin, Christian Jandl, Alexander Poethig, Marco Roverso, Sara Bogialli, Gloria Tabacchi, Ettore Fois, Emanuela Callone, Sandra Dire, Chiara Maccato

Summary: A cobalt complex bearing fluorinated diketonate ligands and a diamine moiety was investigated as a potential Co molecular precursor for the CVD of Co3O4 systems, showing suitability for high-quality Co3O4 thin film fabrication.

DALTON TRANSACTIONS (2021)

Article Chemistry, Organic

Triazolate-based pillarplexes: shape-adaptive metallocavitands via rim modification of macrocyclic ligands

Shengyang Guan, Thomas Pickl, Christian Jandl, Leon Schuchmann, Xiaoyu Zhou, Philipp J. Altmann, Alexander Pothig

Summary: Triazolate-based pillarplexes are a new type of supramolecular organometallic complexes with tubular pores, using a hybrid imidazolium/triazole cyclophane as a ligand precursor. These new pillarplexes show similarities to previously reported pyrazolate-based congeners, but exhibit unprecedented shape-adaptive behavior in the solid-state for the Au(i) complex, rationalized by DFT calculations. Additionally, complementary hydrogen bonding between cationic complexes is observed, demonstrating that rim modification not only modulates cavity flexibility, but also introduces further functionality into the SOC.

ORGANIC CHEMISTRY FRONTIERS (2021)

暂无数据