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Synthesis and spectral luminescent properties of 4,4′,4′′,4′′′-tetra(tert-butyl)-5,5′,5′′,5′′′-tetrakis(phenylsulfanyl)phthalocyanines and their sulfo acids
摘要： Magnesium and zinc complexes of 4,4′,4′′,4′′′-tetra(tert-butyl)-5,5′,5′′,5′′′-tetrakis(phenylsulfanyl)phthalocyanine were synthesized. The corresponding sulfo acids were prepared by sulfochlorination and further hydrolysis. Spectral luminescent properties of the synthesized phthalocyanine derivatives were studied. Introduction of sulfo groups resulted in a bathochromic shift of Q-band in the spectra recorded in DMF and pyridine regardless of the metal nature as well as in a hypsochromic shift in sulfuric acid.
关键词： metal complexes,phthalocyanines,sulfo acids,luminescence
更新于2025-11-14 15:32:45
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Enlightening developments in 1,3-P,N-ligand-stabilized multinuclear complexes: A shift from catalysis to photoluminescence
摘要： 1,3-P,N-ligands provide the ideal spatial separation to facilitate homo and hetero metal-metal interactions to access multinuclear complexes. The rich chemistry of such complexes includes applications in coordination chemistry, metal-activation and (cooperative) catalysis. However, it has been especially the fruitful combination in photoluminescent P,N-coinage metal complexes which has renewed interest in these ligands. While the field classically focused on dinuclear species, now also coinage metal clusters have been studied for use in catalysis and photophysical applications. Reviewed are recent developments from 2009 to mid-2017.
关键词： P,N-ligands,Coinage metal clusters,Photoluminescence,Transition metal complexes,Homogeneous catalysis,Metal-metal bonds
更新于2025-09-23 15:23:52
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Electroluminochromic Materials: From Molecules to Polymers
摘要： Electroluminochromism is an interesting property found in certain classes of molecules and polymers whose photoluminescence can be modulated through the application of an external electrical bias. Unlike electrochromic materials, electroluminochromic counterparts and their applications are comparatively fewer in quantity and are less established. Nonetheless, there prevails an increasing interest in this class of electro-active materials due to their potential applications in optoelectronics, such as smart-displays, and chemical and biological sensing. This review seeks to showcase the different classes of electroluminochromic materials with focus on (i) organic molecules, (ii) transition metal complexes, and (iii) organic polymers. The mechanisms and electroluminochromic performance of these classes of materials are summarized. This review should allow scientists to have a better and deeper understanding of materials design strategies and, more importantly, structure-property relationships and, thus, develops electroluminochromic materials with desired performance in the future.
关键词： metal complexes,electroluminochromic,electrochromic,electrofluorochromic,polymers
更新于2025-09-23 15:22:29
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Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR
摘要： As one of the best studied photoswitches, spiropyrans (SPs) have attracted significant interest in the scientific community. Among the many stimuli to alter the isomerization into the merocyanine (MC) isomer, such as temperature, pH, solvent polarity, redox potential, or mechanical force, the ability of the MC form to act as a ligand site for metal complexation has recently raised new attention. We herein synthesize hitherto undescribed coordination compounds of 8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro-[chromene-2,2′-indoline] with s-block ([Ca(MC)4](ClO4)2), d-block ([Zn(MC)2(MeCN)2](ClO4)2, [Ni(MC)2(MeCN)2](ClO4)2), as well as f-block ([La(NO3)3(MC)2]) metals. All complexes are structurally described by X-ray crystallography and systematically investigated in solution via Job’s method of continuous variations (Job plots), as well as online NMR spectroscopic kinetic experiments with in situ irradiation of the analyte solution inside the NMR spectrometer (LED-NMR). We can unambiguously identify the photoresponsive nature of the complexes in solution, which is a crucial step toward the application of these promising molecules in material science.
关键词： photochemistry,LED-NMR,metal complexes,X-ray crystallography,spiropyrans
更新于2025-09-23 15:19:57
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Infrared + vacuum ultraviolet two-color ionization spectroscopy of neutral metal complexes based on a tunable vacuum ultraviolet free-electron laser
摘要： This paper describes an experimental technique for studying neutral metal complexes using infrared + vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy based on a tunable VUV free-electron laser (VUV-FEL). The preliminary IR spectroscopy results of mass-selected nickel tetracarbonyl are reported in this work. The results demonstrate that the tunable VUV-FEL light allows the selective ionization of a given neutral cluster free of confinement along with the recording of well-resolved IR spectra. As the ionization energies of many neutral clusters are accessible by a broadly tunable VUV-FEL (50–150 nm) and near-threshold ionization can be readily achieved, the proposed experimental method offers unique possibilities for the size-specific study of a wide variety of confinement-free neutral clusters.
关键词： infrared,vacuum ultraviolet,tunable VUV free-electron laser,two-color ionization spectroscopy,neutral metal complexes
更新于2025-09-23 15:19:57
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Singly, Doubly, and Triply Linked Corrole Oligomers: Synthesis, Structures, and Linking Position Dependent Properties
摘要： Direct covalent connections of porphyrinoids have been demonstrated as an effective way to expand their π-electronic networks and perturb their optical and electrochemical properties. Covalent connections are also useful for studies on the precise electronic interaction between two porphyrinoid units. However, the chemistry of covalently linked corrole oligomers lags far behind that of the porphyrin counterparts in spite of the importance of corrole as a ring-contracted porphyrinoid. The lower symmetry of corroles naturally leads to many possible corrole dimers, which have been found to display different optical and electrochemical properties depending on the linking position. In this review, we summarize the synthesis, structures, and properties of corrole oligomers such as singly linked oligomers and fused dimers as well as their metal complexes with a particular focus on their linking position dependent electronic properties.
关键词： excited-state dynamics,oxidation,oligomers,corroles,metal complexes
更新于2025-09-19 17:15:36
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Luminescent Cyclic Trinuclear Coinage Metal Complexes with Aggregation-Induced Emission (AIE) Performance
摘要： A series of AIE active cyclic trinuclear complexes (Au3, Ag3, and Cu3) have been successfully prepared and elucidated by X-ray crystallography. These complexes showed excellent AIE properties and their quantum yields (QYs) were significantly increased compared to that of the free ligands. The remarkable solution induced AIE activity in atom-precise coinage metal complexes is still scarce, and this work opens a promising avenue for the development of easily prepared metal-based AIE luminogens with high emission efficiency.
关键词： Aggregation-Induced Emission,X-ray Crystallography,Quantum Yields,Coinage Metal Complexes,Luminescence
更新于2025-09-19 17:15:36
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Recent advances in circularly polarized electroluminescence based on organic light-emitting diodes
摘要： Since the first attempt that was made to obtain direct circularly polarized (CP) light from OLEDs by Meijer et al. in 1997, considerable efforts have been devoted to the development of circularly polarized organic light-emitting diodes (CP-OLEDs), particularly in the recent years. Circularly polarized electroluminescence (CPEL) based on OLEDs has attracted increasing interest for its efficient ability to generate CP light directly and wide potential applications in 3D displays, optical data storage, and optical spintronics. In this review, we systematically summarize the recent progress in chiral emitter based OLEDs with CPEL properties including CPEL based on chiral conjugated polymers, CPEL based on chiral metal complexes, and CPEL based on chiral simple organic molecules, especially chiral thermally activated delayed fluorescence (TADF) molecules. We believe that this review will provide a promising perspective of chiral emitter based OLEDs with CPEL properties for a broad range of scientists in different disciplinary areas and attract a growing number of researchers to this fast-growing research field.
关键词： chiral simple organic molecules,circularly polarized electroluminescence,thermally activated delayed fluorescence,chiral conjugated polymers,organic light-emitting diodes,chiral metal complexes
更新于2025-09-16 10:30:52
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Spectral Methods in Transition Metal Complexes || Electronic Spectroscopy
摘要： The electronic spectrum covers the range from 200 to 800 nm of the electromagnetic spectrum: 200–400 nm is the ultraviolet region and 400–800 nm is the visible region. Hence, the electronic spectrum is also known as the UV-Vis spectrum. The major application of this spectrum to metal complexes is the determination of the geometry of the complex. In order to arrive at this application, we must understand Term Symbols ?rst. If we want to understand these concepts, selection rules, and transitions, we must have a clear understanding of the concepts of the symmetry of molecules, the symmetry elements, symmetry operations, point groups of molecules, character tables, direct product concepts, and so on. Hence, we will discuss these concepts before the term symbols.
关键词： UV-Vis spectrum,symmetry elements,electronic spectrum,character tables,direct product,Term Symbols,symmetry,metal complexes,point groups,geometry,symmetry operations
更新于2025-09-10 09:29:36
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Transition metal complexes based aptamers as optical diagnostic tools for disease proteins and biomolecules
摘要： Aptamers are powerful recognition elements that can bind a large number of target molecules, including metal ions, small molecules, proteins, enzymes, even complex targets like cancer cells, etc., with high affinity and specificity. Hence, aptamer-based biosensors (hereafter named "aptasensors") have been extensively utilized in the field of clinical diagnostics and biomedical applications. In contrast to organic luminophores and quantum dots, luminescent transition metal complexes offer many desirable and wide-ranging properties, including tunable emission throughout the visible to NIR regions, long lifetime with a large Stockes shift, high quantum yield, good thermal, chemical and photochemical stability and metabolic inertness for biosensing applications. The incorporation of biomolecules or lipophilic entities into the metal complexes could overcome problems associated with membrane permeability and uptake by cells. Especially, Ru(II) and Ir(III) complexes are promising candidates for these potential applications. This review describes an overview of recent progress in the emerging area of aptasensors utilizing Ru(II) and Ir(III) transition metal complexes. To date, though aptasensors have been used in a wide variety of detection techniques, we have focused mainly on the luminescence approach in this article. Numerous aptasensors have illustrated promising detection results, even in complicated biological environments. If more rigorous research is continued on this area, it is hoped that in the future transition metal complexes based aptamers may show tremendous applications in biomedical research, especially diagnostics, imaging and drug delivery.
关键词： Proteins,Biosensor,Metal complexes,Luminescence,Aptamer
更新于2025-09-10 09:29:36