Fluorenyl Radicals Stabilized by Donor‐π‐Radical Conjugation between Nitrogen Atoms and Carbon Radicals DOI
Xinfang Zhang, Zekun Tong, Shaoqiang Dong

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Comprehensive Summary A design strategy towards stable fluorenyl radicals ( FR s) has been developed through introducing donor‐π‐radical (D‐π‐R) conjugation, facilitated by the linkage of amine N atoms and centers via phenyl or 9‐anthryl moieties. Four s, with without atom containing protecting groups, were designed synthesized for comparative analysis. X‐ray crystallographic studies revealed planar skeletons CDP‐FR MA‐FR , which exhibit significant dihedral angles relative to their groups. Wiberg bond‐order analysis natural bond orbital conducted on C‐C C‐N between radical center in all s clearly demonstrated presence D‐π‐R conjugation. Furthermore, time‐dependent DFT calculations, based frontier molecular analysis, highlighted contribution structures as donor‐acceptor effect lowest energy absorptions carbazole diphenylamine substituted DPAA‐FR would promote charge transfer process inhibit photodegradation reaction. Consequently, beneficial from conjugations, exhibited superior photostability compared TP‐FR . Our study offers a new synthesis persistent monoradicals.

Language: Английский

The Impact of Donor‐Orientation on the Emission Properties of Chlorinated Trityl Radicals DOI Creative Commons
Mona E. Arnold,

Robert Toews,

Lars Schneider

et al.

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

Abstract Chlorinated trityl radicals functionalized with electron‐donating groups are promising red‐emitting materials for optoelectronic and spintronic applications, overcoming the spin‐statistical limit of conventional emitters. Donor functionalization induces charge transfer character, enhancing photoluminescence quantum yield, which depends on donor strength its orientation. However, donor‐functionalized tris(trichlorophenyl)methyl often show lower yield than their perchlorinated derivatives, likely due to weaker donor‐acceptor electronic coupling enhanced non‐radiative decay. A novel derivative is presented two additional chlorines that restrict orientation a nearly perpendicular arrangement toward plane, minimizing vibronic losses. Spectroscopic computational studies reveal this steric constraint improves compared analogs. These findings highlight potential decoupling enable efficient, redshifted emission, offering design strategy high‐performance radical

Language: Английский

Citations

0
Electron–electron repulsion in carbazole oligomer-attached tris (2,4,6-trichlorophenyl) methyl radicals DOI

Kenshiro Matsuda,

Wataru Ota,

Keiko Yamaoka

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(16)

Published: April 22, 2025

Luminescent radicals are gathering much attention as a new class of luminescent material. We have synthesized carbazole oligomer (mono, di, tri, tetra) substituted tris (2,4,6-trichlorophenyl) methyl (TTM) radicals. The photoluminescence (PL) spectra showed emission stemmed from the excited state charge transfer character. Despite increase in highest occupied molecular orbital level associated with increasing length, PL maxima blue shift di- to tetra-oligomer substitution. This unexpected behavior was explained by quantum chemical calculations, including electron–electron repulsion. repulsion on donor decreases when length increases and leads emission. accompanied an yield substituting large π-conjugated TTM radical would be unique method control photophysical property radical.

Language: Английский

Citations

0
Influence of Electronic Correlations on Electron–Phonon Interactions of Molecular Systems with the GW and Coupled Cluster Methods DOI
Antonios M. Alvertis, David B. Williams‐Young, Fabien Bruneval

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(14), P. 6175 - 6183

Published: July 2, 2024

Electron-phonon interactions are of great importance to a variety physical phenomena, and their accurate description is an important goal for first-principles calculations. Isolated examples materials molecular systems have emerged where electron-phonon coupling enhanced over density functional theory (DFT) when using the Green's-function-based

Language: Английский

Citations

2
From Coherence to Function: Exploring the Connection in Chemical Systems DOI
Shahnawaz R. Rather, Gregory D. Scholes, Lin X. Chen

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2620 - 2630

Published: Sept. 2, 2024

ConspectusThe role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention the last two decades largely due to advancements ultrafast laser spectroscopy. These coherence effects hold promise for enhancing efficiency and robustness functionally relevant processes, even when confronted with energy disorder environmental fluctuations. Understanding deeply drives us unravel mechanisms dynamics controlled by order synchronization at a level, envisioning optical control enhance functions create new ones molecular material systems. In this frontier, interplay between electronic vibrational dynamics, specifically influence vibrations directing emerged as leading principle. Here, energetically disparate degrees freedom work in-sync dictate trajectory an reaction. Moreover, degree being directly related structural composition systems, designs could be inspired tailoring certain elements.In realm chemical kinetics, our understanding transformations is underpinned fundamental theories, such transition theory, activated rate Marcus theory. theories elucidate reaction rates considering barriers that must overcome reactants transform into products. Those are surmounted stochastic nature gap fluctuations within reacting emphasizing coordinate, pathway from products, not rigidly defined specific motion but encompasses diverse array motions. While less known about involvement intramolecular modes, their significance cases cannot overlooked.In Account, we summarize key experimental findings offer deeper insights complex electronic-vibrational trajectories encompassing afforded state-of-the-art spectroscopy three exemplary processes: photoinduced electron transfer, singlet-triplet intersystem crossing, flow We delve rapid decoherence, loss phase amplitude correlations, along promoter during subpicosecond crossing series binuclear platinum complexes. This decoherence illustrates vibration-driven reactive pathways Franck-Condon curve region. also explore generation induced impulsive rather than pulse these which sheds light on dissipation thereby progression vicinity product side. Another property coherences, amplitude, reveals how can one vibration another terpyridine-molybdenum hosting nonreactive dinitrogen substrate. A slight change triggers quasi-resonant interaction, constructive wavepacket interference ultimately redistribution active terpyridine stretching vibration, energizing bond.

Language: Английский

Citations

2
Insights into the vibration coupling effects on reorganization energy in π-isoelectronic frameworks DOI Creative Commons
Yanan Zhu, Xing Xing,

Chongguang Zhao

et al.

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(27), P. 9950 - 9956

Published: Jan. 1, 2024

This study delves into the intricate interplay of vibrational coupling within isoelectronic frameworks featuring both zigzag and armchair topologies, aiming to better understand topological heteroatom impacts on reorganization energy.

Language: Английский

Citations

1
Lattice Dynamics of Quasi-2D Perovskites from First Principles DOI Creative Commons
Emily Y. Chen, Bartomeu Monserrat

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: unknown

Published: July 16, 2024

We present the vibrational properties and phonon dispersion for quasi-2D hybrid organic–inorganic perovskites (BA)2CsPb2I7, (HA)2CsPb2I7, (BA)2(MA)Pb2I7, (HA)2(MA)Pb2I7 calculated from first principles. Given highly complex nature of these compounds, we perform careful benchmarking convergence testing to identify suitable parameters describe their structural features properties. find that inclusion van der Waals corrections on top generalized gradient approximation (GGA) exchange-correlation functionals provides best agreement equilibrium structure relative experimental data. also investigate impact molecular orientation layered perovskite systems. Our results suggest ground state ferroelectric alignment dipoles in out-of-plane direction is unlikely support assignment centrosymmetric space group low-temperature phase (HA)2(MA)Pb2I7. Finally, compute under harmonic approximation. stringent energy cut-offs are required obtain well-converged properties, once converged, can capture key physics such a large, inorganic–organic system with vastly different atom types, masses, interatomic interactions. discuss obtained modes behavior context known bulk 3D ligand crystals. While many inherited parent systems, observe unique coupled vibrations cannot be associated pure constituent subphases. Energy low branches primarily occurs in-plane within subphase arises bending breathing equatorial Pb–I network octahedral plane. The analysis herein foundation future investigations this class materials, as exciton–phonon coupling, transitions, general temperature-dependent

Language: Английский

Citations

1
Thiophene-fused aromatic belts DOI Creative Commons
Hiroki Shudo,

Philipp Wiesener,

Elena Kolodzeiski

et al.

Published: July 30, 2024

Aromatic belts, ultrashort carbon nanotubes and related structures, are emerging molecular entities in the fields of organic electronics supramolecular chemistry owing to their structural rigidity, fully fused π-conjugation, well-defined cavity. Synthesis aromatic belts with embedded thiophene which manifest significant optoelectronic conductive properties, has not yet been achieved. Herein, we report synthesis long sought-after thiophene-fused (thiophene belts) via one-step sulfur cross-linking reaction partially fluorinated cycloparaphenylenes. Their unique features, including unidirectional columnar stacking high dipole moment crystals, two-dimensional layer assembly on metal surfaces, photophysical such as long-lifetime phosphorescence, were uncovered. These distinctive features should inspire a range applications next-generation devices polar materials.

Language: Английский

Citations

1
Temperature driven shifts of super-conductance in Zn-doped CuTl-1223 nanoparticle DOI
Muhammad Aamir, Muhammad Waseem Mumtaz,

Iqrar Saqib

et al.

Journal of Materials Science Materials in Electronics, Journal Year: 2024, Volume and Issue: 35(33)

Published: Nov. 1, 2024

Language: Английский

Citations

1
Vibration isolation could boost performance of near-infrared organic LEDs DOI
Margherita Maiuri

Nature, Journal Year: 2024, Volume and Issue: 629(8011), P. 289 - 290

Published: May 8, 2024

Language: Английский

Citations

0
Highly Efficient Near‐Infrared Luminescent Radicals with Emission Peaks over 750 nm DOI

Chunxiao Wu,

Lu Chen, Shilong Yu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 2, 2024

Abstract Purely organic molecules exhibiting near‐infrared (NIR) emission possess considerable potential for applications in both biological and optoelectronic technological domains, owing to their inherent advantages such as cost‐effectiveness, biocompatibility, facile chemical modifiability. However, the repertoire of with peaks exceeding 750 nm concurrently demonstrating high photoluminescence quantum efficiency (PLQE) remains relatively scarce due energy gap law. Herein, we report two open‐shell NIR radical emitters, denoted DMNA‐Cz‐BTM DMNA‐PyID‐BTM, achieved through strategic integration a donor group (DMNA) onto Cz‐BTM PyID‐BTM frameworks, respectively. We found that donor‐acceptor molecular structure allows designed emitters exhibit charge‐transfer excited state spatially separated electron hole levels non‐bonding characteristics. Thus, high‐frequency vibrations are effectively suppressed. Besides, reduction low‐frequency is observed. Collectively, non‐radiative decay channel significantly suppressed, leading exceptional PLQE values. Specifically, manifests an peak at 758 alongside 55 %, whereas DMNA‐PyID‐BTM exhibits 778 66 %. Notably, these represent pinnacle among metal‐free surpassing nm.

Language: Английский

Citations

0