High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 19, 2024

A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi-bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post-synthetic transformation in the solid-state, affording C. Thermogravimetric analysis, IR spectroscopy and single-crystal X-ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye-perceived green (B) to blue (C) room-temperature luminescence for these molecular solids. Photophysical measurements time-dependent density-functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli-sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

Noncovalent Interactions in Coordination Chemistry of Cyclic Trinuclear Copper(I) and Silver(I) Pyrazolates DOI Creative Commons

Arina Olbrykh,

Gleb B. Yakovlev,

Aleksei A. Titov

et al.

Crystals, Journal Year: 2025, Volume and Issue: 15(2), P. 115 - 115

Published: Jan. 23, 2025

Group 11 metals form with pyrazolate ligand complexes a general formula of [MPz]n. The value “n” varies depending on the type substituent in and metal atom. Copper(I) silver(I) ions mainly cyclic di-, tri-, tetra-nuclear or polymeric structures. Cyclic trinuclear d10 pyrazolates [MPzm]3 (M = Cu(I) Ag(I); Pz substituted ligand) are particular interest because their planar structure allows them to supramolecular aggregates via noncovalent metal–metal, metal–π, metal–electron donor interactions. Designing based these interactions has been focus research for last two decades. ability copper(I) coordination structures determines properties potential applications catalysis, gas sensing, molecular recognition, photoluminescence. In this review, we discuss between various types ligands.

Language: Английский

Citations

0
Enabling Thermally Stimulated Delayed Phosphorescence in Cu(I) Cyclic Trinuclear Complexes with Near-Unity Quantum Yield DOI

Guo‐Quan Huang,

Ri‐Qin Xia, Xu Chen

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Thermally stimulated delayed phosphorescence (TSDP) emission has recently been discovered in several Au(I)/Au(III) complexes, featuring thermally enhanced intensities and notable quantum yields (QYs). Developing earth-abundant metal-based TSDP emitters with further increased QYs holds significant promise for practical applications. Herein, we present a halogen bonding approach to achieve bromo-substituted Cu(I) cyclic trinuclear complexes (CTCs). Photophysical analysis theoretical calculations reveal the crucial role of suppressing excited-state distortions reducing energy differences between first second triplet excited states (T1 T2). This enables efficient spin-allowed reverse internal conversion, leading behavior. Additionally, low reorganization rigid halogen-bonded network CTCs result significantly suppressed nonradiative decay high QYs, one approaching near-unity. work provides an innovative extend behavior from QYs.

Language: Английский

Citations

0
A Series of Luminescent [(Xantphos)CuILN] Complexes and Their Luminescence Sensing Properties for VOCs Detection and TD‐DFT Calculation DOI

Yifan Jia,

Li Song, Jianmin Chen

et al.

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(5)

Published: April 9, 2025

ABSTRACT The design and research of luminescent volatile organic compounds (VOCs) fluorescent sensing/stimuli–response materials are great significance challenge. We report herein a series new [(Xantphos)CuIL N ] type complexes with tetrahedral CuIP 2 coordination, showing luminescence from blue to red sensing for VOCs detection (Xantphos is 4,5‐bis (diphenylphosphino)‐9,9‐dimethylxanthene, L N‐containing ligand). Firstly, six 1 – 6 were designed ball‐milling synthesized by the ligand‐addition reaction raw material [(Xantphos)CuI] different ligands 2‐aminopyridine ( ), 3‐cyanopyridine 4‐cyanopyridine 3 2‐(3′‐pyridyl)‐benzoxazole 4 3‐I‐4‐aminopyridine 5 imidazole ). Time‐dependent density functional theory (TD‐DFT) calculations assign low‐energy band (absorption edge) in UV–Vis absorption as mixed (XL + ML)CT transition, corresponding excited state also thought be source photoluminescence (PL). Material has highest PL efficiency (~44%), which may benefit its greatest structural rigidity. exhibiting worst should related iodine atom ligand (I dominate unoccupied orbitals S T states). Based on very weak PL, thin‐film sensor ) achieve significantly enhanced (lighting‐up mode) pyridine 4‐methylpyridine vapor. achieves lowest limit (LOD = 2.51 ppm) fastest response speed (T 50 30 s) pyridine. In addition, show interesting quenching vapochromic variety vapors.

Language: Английский

Citations

0
Advanced anticounterfeiting polymer inks for high-level encryption and authentication technologies DOI

Reza Khalilzadeh,

Milad Babazadeh‐Mamaqani,

Moein Mohammadi‐Jorjafki

et al.

Progress in Materials Science, Journal Year: 2025, Volume and Issue: unknown, P. 101487 - 101487

Published: April 1, 2025

Language: Английский

Citations

0
Recoverable and Sensitive Pressure-Induced Mechanochromic Photoluminescence of a Au-P Complex DOI Creative Commons

Ningwen Yang,

Y. C. Chang,

Jiangyue Wang

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(9), P. 2011 - 2011

Published: April 30, 2025

A binuclear Au-P complex [Au2(2-bdppmapy)2](PF6)2 (1) was synthesised by the reaction of 2-bdppmapy (N,N′-bis-(diphenylphosphanylmethyl-2-aminopyridine) with AuCN and [Cu(MeCN)4]PF6. The solid phase 1 emitted bright yellow phosphorescence at λmax = 580 nm under UV excitation (QY 4.41%, τ 1.88 μs), which shifted to green (λmax 551 nm, QY 5.73%) after being pressurised 5 MPa. This colour change recoverable upon exposure CH2Cl2 vapor. Similar mechanochromic photoluminescence behaviour observed grinding crystals 1. filter paper impregnated demonstrated recyclable write/erase functionality for encrypted information transfer.

Language: Английский

Citations

0
The crystal structure of catena-poly(μ2-1,4-bis-(1H-imidazol-1-yl)benzene-copper(I)) dichloridocopper(I), {[CuC12H10N4]+[CuCl2]−} n DOI Creative Commons
Airong Wang,

Hangyi An,

Xiaoli Wang

et al.

Zeitschrift für Kristallographie - New Crystal Structures, Journal Year: 2024, Volume and Issue: 239(4), P. 751 - 754

Published: June 18, 2024

Abstract [CuC 12 H 10 N 4 ]⋅[CuCl 2 ], triclinic, P 1̄ (no. 2), a = 4.2957(9) Å, b 8.718(2) c 9.878(3) α 67.58(2)°, β 78.97(2)°, γ 80.043(19)°, V 333.63(15) Å 3 , Z 1, R gt ( F ) 0.0360, wR ref 0.0998, T 296 K.

Language: Английский

Citations

0
High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 19, 2024

Abstract A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi‐bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post‐synthetic transformation in the solid‐state, affording C . Thermogravimetric analysis, IR spectroscopy and single‐crystal X‐ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye‐perceived green ( ) to blue room‐temperature luminescence for these molecular solids. Photophysical measurements time‐dependent density‐functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli‐sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

Citations

0
High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 19, 2024

A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi-bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post-synthetic transformation in the solid-state, affording C. Thermogravimetric analysis, IR spectroscopy and single-crystal X-ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye-perceived green (B) to blue (C) room-temperature luminescence for these molecular solids. Photophysical measurements time-dependent density-functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli-sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

Citations

0