Figure - available from: Aggregate
This content is subject to copyright. Terms and conditions apply.
![Circularly polarized luminescence (CPL) probes of metal complexes. (A) (i) Structure of racemic 46, (ii and iii) optimized structure of (ii) (Λ)‐[46·Zn·AMP] and (iii) (Δ)‐[46·Zn·ATP] aggregate, and (iv) their CPL spectra. Reproduced with permission: Copyright 2018, John Wiley and Sons.[¹¹⁷] (B) CPL spectra of racemic 47 upon forming aggregates with bovine or human α1‐AGP at pH of 9.3. Reproduced with permission: Copyright 2018, The Royal Society of Chemistry.[¹¹⁸] (C) CPL spectra of (S,S,S)‐Δ‐48 with gradual addition of bovine serum albumin (BSA). Reproduced with permission: Copyright 2008, The Royal Society of Chemistry[¹²²]](publication/358529331/figure/fig10/AS:11431281181620925@1692117941122/Circularly-polarized-luminescence-CPL-probes-of-metal-complexes-A-i-Structure-of.png)
Circularly polarized luminescence (CPL) probes of metal complexes. (A) (i) Structure of racemic 46, (ii and iii) optimized structure of (ii) (Λ)‐[46·Zn·AMP] and (iii) (Δ)‐[46·Zn·ATP] aggregate, and (iv) their CPL spectra. Reproduced with permission: Copyright 2018, John Wiley and Sons.[¹¹⁷] (B) CPL spectra of racemic 47 upon forming aggregates with bovine or human α1‐AGP at pH of 9.3. Reproduced with permission: Copyright 2018, The Royal Society of Chemistry.[¹¹⁸] (C) CPL spectra of (S,S,S)‐Δ‐48 with gradual addition of bovine serum albumin (BSA). Reproduced with permission: Copyright 2008, The Royal Society of Chemistry[¹²²]
Source publication
The development and applications of materials with efficient circularly polarized luminescence (CPL) have become an interdisciplinary frontier research topic. We summarize herein the recent advance in the development and applications of CPL‐active aggregates based on metal‐ligand coordination materials (termed as “coordination aggregates”). The mat...
Similar publications
Iron ion is widely present in the environment and in biological systems, and are indispensable trace elements in living organisms, so development of an efficient and simple sensor for sensing Fe(III) ions has attracted much attention. Here, six heterometallic AE-Ln coordination polymers (CPs) [Ln2 (pda)4(Hnda)2Ca2(H2O)2]·MeOH (Ln = Eu (1), Tb (2);...
The possibility of obtaining volatile polynuclear heterometallic complexes containing lanthanides and transition metals bound by methoxy-β-diketonates was studied. New compounds were prepared by cocrystallization of monometallic complexes from organic solvents. Ln(tmhd)3 were used as initial monometallic complexes (Ln = La, Pr, Sm, Gd, Tb, Dy, Lu;...
Citations
Circularly polarized luminescence (CPL)‐active molecular materials have drawn increasing attention due to their promising applications for next‐generation display and optoelectronic technologies. Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor ( g lum ) and high quantum yield ( Φ ). A pair of enantiomeric N N C‐type Pt(II) complexes ( L/D )‐ 1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL‐inactive, the spin‐coated thin films of ( L/D )‐ 1 exhibit giantly‐amplified circularly polarized phosphorescences with | g lum | of 0.53 at 560 nm and Φ air of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor | g abs | of 0.37–0.43 at 480 nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes ( L/D )‐ 2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of ( L/D )‐ 1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of ( L/D )‐ 1 in CPL‐contrast imaging and inducing CP light generation from achiral emitters and common light‐emitting diode lamps have been successfully realized.
Recent advances in the design of AIE platinum complexes: structural regulation strategies, mechanisms, and applications.
Herein, it is reported that lyotropic liquid crystals that transfer carbon‐centered chirality to helical chirality and subsequently to macroscopic chirality in the mesophases. This process is accompanied by remarkable amplification of both emission quantum yield and dissymmetry factor of the circularly polarized luminescence (CPL). Cationic tridentate cyclometalated Pd(II) complexes, once functionalized with chiral hydrogen‐bonding motifs of amide, aggregated into head‐to‐tail dimers at low concentrations in acetonitrile and further self‐organized into chiral lyotropic chromonic mesophases upon concentrated to 50 wt.%. At 25 °C, the chiral chromonics display metal–metal‐to‐ligand charge‐transfer (MMLCT) phosphorescence at an emission maximum of 677 nm with quantum yields up to 38% and lifetimes up to 0.50 µs. Notably, the dissymmetry factors ranged from 0.10 to 0.76, varying with the sample thickness in the range of 200–15 µm. Comparison studies and theoretical calculations reveal that the hydrogen‐bonding amide group is pivotal for the formation of the staggered configuration in the helical superstructures. Additionally, the carbon‐centered chirality of the amide dictate the handedness of the helices and consequently influenced the properties of CPL.
Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C14, demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C14 became more circular to better accommodate spherical fullerene molecules. The host−guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C14 shows stronger binding with C70 than with C60 due to the better convex−concave π−π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.
Circularly polarized luminescence (CPL)‐active molecular materials have drawn increasing attention due to their promising applications for next‐generation display and optoelectronic technologies. Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor (glum) and high quantum yield (Φ). A pair of enantiomeric N N C‐type Pt(II) complexes (L/D)‐1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL‐inactive, the spin‐coated thin films of (L/D)‐1 exhibit giantly‐amplified circularly polarized phosphorescences with |glum| of 0.53 at 560 nm and Φair of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor |gabs| of 0.37–0.43 at 480 nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes (L/D)‐2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of (L/D)‐1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of (L/D)‐1 in CPL‐contrast imaging and inducing CP light generation from achiral emitters and common light‐emitting diode lamps have been successfully realized.
Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self‐assembly of amphiphilic phosphorescent platinum(II) complexes (L‐Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self‐assembly of L‐Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15% at 25 °C to 53% at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04 × 10‐2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L‐Pt molecules. Importantly, the QY and glum of the L‐Pt assembly in solid state were measured as 69% and 0.16 respectively, representing relatively high values compared to most self‐assembled CPL systems. This study marks the pioneering demonstration of dual thermo‐enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high‐temperature and switchable CPL materials.
Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self‐assembly of amphiphilic phosphorescent platinum(II) complexes (L−Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self‐assembly of L−Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10⁻² to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L−Pt molecules. Importantly, the QY and glum of the L−Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self‐assembled CPL systems. This study marks the pioneering demonstration of dual thermo‐enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high‐temperature and switchable CPL materials.
