Intramolecular Through‐Space Charge‐Transfer Effect for Achieving Room‐Temperature Phosphorescence in Amorphous Film DOI Creative Commons
Dehai Dou, Xin Zhou, Tian Wang

et al.

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Abstract Organic emitters that exhibit room‐temperature phosphorescence (RTP) in neat films have application potential for optoelectronic devices, bio‐imaging, and sensing. Due to molecular vibrations or rotations, the majority of triplet excitons recombine rapidly via non‐radiative processes purely organic emitters, making it challenging observe RTP amorphous films. Here, a chemical strategy enhance is reported, by utilizing through‐space charge‐transfer (TSCT) effect induced intramolecular steric hindrance. The donor acceptor groups interact spatial orbital overlaps, while motions are suppressed simultaneously. As result, triplets generated under photo‐excitation stabilized films, contributing even at room temperature. solvatochromic on steady‐state transient photoluminescence reveals feature involved excited states, TSCT further experimentally resolved femtosecond absorption spectroscopy. designed luminescent materials with pronounced show lifetimes up ≈40 ms, comparable rigid polymer host. Photoluminescence afterglow longer than 3 s observed Therefore, demonstrated hindrance stabilize long‐lived leads

Language: Английский

Luminescent N^C^N Pincer Ni(II), Pd(II), and Pt(II) Complexes with a Pendant Coumarin Group: The Role of Auxiliary Ligands and Environments DOI
Dominik Moreth, María Victoria Cappellari,

Andreas Müller

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

Square-planar d8-configured metal complexes and their excited states play a key role in photocatalysis, sensing, optoelectronic devices. However, metal-to-ligand charge-transfer (MLCT) involving transition metals, particularly those with 3d8 electronic configuration, present challenges due to rapid nonradiative relaxation via low-lying metal-centered (MC) states. In this work, an isoelectronic isostructural series of cyclometalated [MX(dpb)] M = Ni(II), Pd(II), Pt(II), dpb 1,3-di(2-pyridyl)phenide, auxiliary ligand X chlorido, azido, triazolato were studied by UV/vis absorption, steady-state, time-resolved photoluminescence spectroscopy solution frozen glassy matrix at 77 K, along DFT calculations. Consistently, the Pd(II) Pt(II) exhibited characteristic emission from triplet ligand-centered (3LC) contrast, Ni(II) triazolatoCOOCH3,COOCH3 ligands nonemissive low room temperatures, presence MC-type ligand-field On other hand, [Ni(triazolatoCoumarin,COOCH3)(dpb)] showed phosphorescence T5 state since restrictive environment limits structural relaxation, while temperature, primary is singlet LC coumarin moiety free ligand.

Language: Английский

Citations

3
Tuning the Terminal N* and C^ Moieties Toward Tailored Pt(II) Complexes with Thiazole-Based N*N^C Luminophores DOI
Stefan Buss, Leon Geerkens, Rose Jordan

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

Citations

1
A stereodynamic probe of Pt(II) molecular hinge for chiroptical sensing of cryptochiral compounds DOI Creative Commons
Yeye Ai, Yinghao Zhang, Ying Jiang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 25, 2025

Cryptochiral compounds are indispensable in biology systems and medical applications, yet the development of high-performance detection method remains challenging. Here, we report a hinge-like dinuclear Pt(II) complex as stereodynamic probe for cryptochirality sensing. This features constrained, closed conformation achieved through synergistic intramolecular π − stacking metal-metal interactions between cyclometalated wings. The shows robust chiroptical response to center-to-axial chiral induction during rapid condensation with cryptochiral that adopts more energetically favorable conformation. resulting intense Cotton effects at long wavelengths enable in-situ circular dichroism analysis determinate absolute configuration enantiometric composition molecules. Furthermore, near-infrared phosphorescence characteristics hinge have been explored develop it an optical sensor accurate quantification With its dual CD capabilities, this great potential high-throughput screening analysis. authors complexes probes

Language: Английский

Citations

1
Room‐Temperature Near‐Infrared Phosphorescence from C64 Nanographene Tetraimide by π‐Stacking Complexation with Platinum Porphyrin DOI Creative Commons
M. A. Niyas, Swadhin Garain, Kazutaka Shoyama

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 7, 2024

Abstract Near‐Infrared (NIR) phosphorescence at room temperature is challenging to achieve for organic molecules due negligible spin–orbit coupling and a low energy gap leading fast non‐radiative transitions. Here, we show supramolecular host–guest strategy harvest the from low‐lying triplet state of C 64 nanographene tetraimide 1 . H NMR X‐ray analysis confirmed : 2 stoichiometric binding Pt(II) porphyrin on two π‐surfaces While free does not emission in NIR, complex solution shows NIR 77 K. Further, between 860–1100 nm, ( λ max =900 τ avg =142 μs) was observed solid‐state sample drop‐casted preformed solution. Theoretical calculations reveal non‐zero isoenergetic S T 3 π‐stacked [ ⋅ porphyrin] complex. External heavy‐atom‐induced along with rigidification protection oxygen promotes both intersystem crossing first excited singlet into manifold lowest

Language: Английский

Citations

6
Simultaneous Thermally Stimulated Delayed Phosphorescence (TSDP) and Thermally Activated Delayed Fluorescence (TADF) in a Two-Coordinated Au(I) Bimetallic Complex Featuring a Tandem Carbene Structure DOI

Shu-Jia Zheng,

Jie Ma,

Junru Su

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19042 - 19049

Published: July 1, 2024

A bimetallic, two-coordinated carbene-metal-amine (cMa) Au(I) complex featuring a twisted tandem carbene structure (NHC1-Au-NHC2-Au-carbazolyl) was synthesized. The molecular in single crystals revealed large dihedral angle between the two ligands, while bridged NHC2 and carbazolyl (Cz) ligands were coplanar. bluish green thermally stimulated delayed phosphorescence (TSDP) observed with an emission lifetime over 70 μs, which can be attributed to spin allowed diabatic population of high-lying emissive triplet state from 3LE characterized low-lying ones. small rotation energy barrier Cz along coordination bond conformers angles Cz. ICT S1 consequently stabilized achieve accessible gap facilitate ISC triplets S1, leading activated fluorescence (TADF). Simultaneous TSDP TADF dual recorded its doped polymer film owing coexistence these different conformers.

Language: Английский

Citations

6
Spin in Organic Cocrystals DOI
Cheng Zhang, Xin Wang, Yang Li

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(32)

Published: March 14, 2023

Organic spintronics has caused a huge revolution in creating highly efficient low-power circuits. Spin manipulation organic cocrystals become promising strategy to uncover more chemicophysical properties for diverse applications. In this Minireview, we summarize the recent advancements of spin charge-transfer cocrystals, and briefly describe possible mechanisms behind them. Beside known (spin multiplicity, mechanoresponsive spin, chiral orbit spin-crossover) binary/ternary other phenomena radical transport are also summarized discussed. Hopefully, deep understanding current achievements, challenges perspectives will offer clear direction introduction cocrystals.

Language: Английский

Citations

12
Exploring multi-stimuli-responsive Pt(ii) complexes: supramolecular self-assembly, lysosome-specific targeted photodynamic therapy and photodegradation of organic pollutants DOI
Hui Ding,

Xiepeng Deng,

Xiang Liu

et al.

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1693 - 1702

Published: Jan. 1, 2024

Developing novel luminescent materials with multi-stimuli-responsiveness and multi-functional properties is vital.

Language: Английский

Citations

4
Phosphorescent Cyclometalated Palladium(II) and Platinum(II) Complexes Derived from Diaminocarbene Precursors DOI Creative Commons
Maria V. Kashina, Konstantin V. Luzyanin, Dmitry Dar’in

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(12), P. 5315 - 5319

Published: March 12, 2024

Metal-mediated self-assembly of isocyanides and methyl 4-aminopyrimidine-5-carboxylate leads to luminescent PdII PtII complexes featuring C,N-cyclometalated acyclic diaminocarbene (ADC) ligands. The solid-state properties these derivatives are attributed their triplet-state metal/metal-to-ligand charge-transfer (3MMLCT) nature, which is driven by attractive intermolecular M···M interactions further reinforced the intramolecular π–π even in structure Pd compound, first Pd-ADC phosphor reported.

Language: Английский

Citations

4
N,C,N-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal–Metal Bond and the Photophysical Properties DOI
Miguel A. Esteruelas,

Sonia Moreno-Blázquez,

Montserrat Oliván

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 19, 2024

Precursors PtCl{κ

Language: Английский

Citations

4
Reversible Piezochromism of Platinum(II) and Palladium(II) Dimers in Molecular Single Crystals DOI
Paul Steeger, Tobias Theiss,

Dominik Schwab

et al.

Nano Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Transition metal complexes are well-known for their efficient light emission and promising applications ranging from bioimaging to light-emitting diodes. In solution, interactions between the centers of two become possible drastically change photophysical properties. For real-world devices, solid-state materials consisting these molecules preferable. Recently, ligand-controlled aggregation platinum(II) palladium(II) into molecular single crystals controlled formation metal-metal contacts have been demonstrated. Here, we show how distance can be tuned in a way by exerting pressure on crystal. Using optical spectroscopy inside diamond anvil cell, find strong reversible piezochromism up 18 GPa. time-dependent density functional theory, attribute wavelength shift reduction enhanced π orbital overlap dimers.

Language: Английский

Citations

0