Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State DOI
Haoxin Guo, Joshua Bennett Lovell,

Chan Shu

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9422 - 9433

Опубликована: Март 19, 2024

We report a neutral high-spin diradical of chiral C2-symmetric bis[5]diazahelicene with ΔEST ≈ 0.4 kcal mol–1, as determined by EPR spectroscopy/SQUID magnetometry. The is the most persistent among all aminyl radicals reported to date factor 20, half-life up 6 days in 2-MeTHF at room temperature. Its triplet ground state and excellent persistence may be associated unique spin density distribution within dihydrophenazine moiety, which characterizes two effective 3-electron C–N bonds analogous N–O bond nitroxide radical. enantiomerically enriched (ee ≥ 94%) (MM)- (PP)-enantiomers precursors diradicals are obtained either preparative supercritical fluid chromatography or resolution via functionalization auxiliary racemic tetraamine. barrier for racemization solid tetraamine ΔG‡ = 43 ± 0.01 mol–1 483–523 K range. experimentally estimated lower limit diradical, 26 293 K, comparable DFT-determined 31 gas phase 298 K. While pure displays strong chiroptical properties, anisotropy |g| |Δε|/ε 0.036 376 nm, 0.005 548 nm that recently ground-state dication. Notably, radical anion intermediate generation exhibits large SOMO-HOMO inversion, SHI 35 mol–1.

Язык: Английский

Chiral Induced Spin Selectivity DOI Creative Commons
Brian P. Bloom, Yossi Paltiel, Ron Naaman

и другие.

Chemical Reviews, Год журнала: 2024, Номер 124(4), С. 1950 - 1991

Опубликована: Фев. 16, 2024

Since the initial landmark study on chiral induced spin selectivity (CISS) effect in 1999, considerable experimental and theoretical efforts have been made to understand physical underpinnings mechanistic features of this interesting phenomenon. As first formulated, CISS refers innate ability materials act as filters for electron transport; however, more recent experiments demonstrate that displacement currents arising from charge polarization molecules lead without need net flow. With its identification a fundamental connection between symmetry materials, promises profound ubiquitous implications existing technologies new approaches answering age old questions, such homochiral nature life. This review begins with discussion different methods measuring then provides comprehensive overview known exhibit CISS-based phenomena before proceeding identify structure-property relations delineate leading models effect. Next, it identifies some physics, chemistry, biology. The ends critical assessment field comments future outlook.

Язык: Английский

Процитировано

130
Materials for chiral light control DOI
Jeanne Crassous, Matthew J. Fuchter, Danna E. Freedman

и другие.

Nature Reviews Materials, Год журнала: 2023, Номер 8(6), С. 365 - 371

Опубликована: Март 13, 2023

Язык: Английский

Процитировано

119
Self-assembled stereomutation with supramolecular chirality inversion DOI
Guofeng Liu, Mark G. Humphrey, Chi Zhang

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(13), С. 4443 - 4487

Опубликована: Янв. 1, 2023

Supramolecular chirality inversion is closely related to biological and chemical self-assembly systems. This review highlights the fundamental principles, various strategies, promising applications of supramolecular inversion.

Язык: Английский

Процитировано

85
Chiral supramolecular polymers DOI Creative Commons
Fátima García, Rafael Gómez, Luis Sánchez

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(21), С. 7524 - 7548

Опубликована: Янв. 1, 2023

Within the field of supramolecular polymers, chiral polymers are an excellent benchmark to generate helical structures that can clarify origin homochirality in Nature or find out new exciting functionalities organic materials.

Язык: Английский

Процитировано

76
Chirality‐Induced Spin Selectivity: An Enabling Technology for Quantum Applications DOI Creative Commons
Alessandro Chiesa, Alberto Privitera, Emilio Macaluso

и другие.

Advanced Materials, Год журнала: 2023, Номер 35(28)

Опубликована: Май 12, 2023

Molecular spins are promising building blocks of future quantum technologies thanks to the unparalleled flexibility provided by chemistry, which allows design complex structures targeted for specific applications. However, their weak interaction with external stimuli makes it difficult access state at single-molecule level, a fundamental tool use, example, in computing and sensing. Here, an innovative solution exploiting interplay between chirality magnetism using chirality-induced spin selectivity effect on electron transfer processes is foreseen. It envisioned use spin-to-charge conversion mechanism that can be realized connecting molecular qubit dyad where donor acceptor linked chiral bridge. By numerical simulations based realistic parameters, shown could enable initialization, manipulation, single-spin readout qubits qudits even relatively high temperatures.

Язык: Английский

Процитировано

67
Circularly polarized luminescence of helicenes: A data‐informed insight DOI Creative Commons

Matteo Cei,

Lorenzo Di Bari, Francesco Zinna

и другие.

Chirality, Год журнала: 2023, Номер 35(4), С. 192 - 210

Опубликована: Янв. 27, 2023

Abstract Helicenes are an interesting scaffold for chiroptical properties and in particular circularly polarized luminescence (CPL). In this short review, we collect the (g lum ) absorption abs dissymmetry factors associated to first Cotton effect of electronic circular dichroism (ECD) spectrum. Considering data 170 [n]‐helicenes ( n = 4–11), overall found reasonable correlations between g . Despite a few notable exceptions, would confirm similarity stereochemistry ground emitting excited states most helicenes. These results may be useful rationalizing help chemists designing new helicene structures with desired CPL properties.

Язык: Английский

Процитировано

64
Helical Bilayer Nanographenes: Impact of the Helicene Length on the Structural, Electrochemical, Photophysical, and Chiroptical Properties DOI Creative Commons
Patricia Izquierdo‐García, Jesús M. Fernández‐García, Samara Medina Rivero

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11599 - 11610

Опубликована: Май 2, 2023

Helical bilayer nanographenes (HBNGs) are chiral π-extended aromatic compounds consisting of two π-π stacked hexabenzocoronenes (HBCs) joined by a helicene, thus resembling van der Waals layered 2D materials. Herein, we compare [9]HBNG, [10]HBNG, and [11]HBNG helical bilayers endowed with [9], [10], [11]helicenes embedded in their structure, respectively. Interestingly, the helicene length defines overlapping degree between HBCs (number benzene rings involved interactions layers), being 26, 14, 10 rings, respectively, according to X-ray analysis. Unexpectedly, electrochemical study shows that lesser system [9]HBNG strongest electron donor character, part interlayer exchange resonance, more red-shifted values emission. Furthermore, also exceptional chiroptical properties biggest gabs glum (3.6 × 10-2) when compared [10]HBNG owing fine alignment configuration its electric magnetic dipole transition moments. spectroelectrochemical studies as well fluorescence spectroscopy support aforementioned experimental findings, confirming strong impact on this new family nanographenes.

Язык: Английский

Процитировано

57
Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations DOI
Fei Zhao, Jingyi Zhao,

Houting Liu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 10092 - 10103

Опубликована: Апрель 26, 2023

Highly emissive π-conjugated macrocycles with tunable circularly polarized luminescence (CPL) have sparked theoretical and synthetic interests in recent years. Herein, we report a approach to obtain new chiral organoborane (CMC1, CMC2, CMC3) that are built on the structurally [5]helicenes highly luminescent triarylborane/amine moieties embedded into cyclic systems. These rarely accessible B/N-doped main-group show unique topology dependence of optoelectronic chiroptical properties. CMC1 CMC2 higher dissymmetry factor (glum) together an enhanced CPL brightness (BCPL) as compared CMC3. Electronic effects were also tuned resulted bathochromic shifts their emission responses from blue for near-infrared (NIR) region Furthermore, chemical oxidations N donor sites gave rise stable radical cation (CMC1·+SbF6–) diradical dication species (CMC12·2+2SbF6–) serve rare example positively charged open-shell macrocycle.

Язык: Английский

Процитировано

45
Highly Conductive Topologically Chiral Molecular Knots as Efficient Spin Filters DOI Creative Commons
Danyang Zhang, Yutao Sang, Tapan Kumar Das

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26791 - 26798

Опубликована: Ноя. 16, 2023

Knot-like structures were found to have interesting magnetic properties in condensed matter physics. Herein, we report on topologically chiral molecular knots as efficient spintronic material. The discovery of the chiral-induced spin selectivity (CISS) effect opens possibility manipulating orientation with soft materials at room temperature and eliminating need for a ferromagnetic electrode. In trefoil knot, there are no stereogenic carbon atoms, chirality results from spatial arrangements crossings knot structures. molecules show very high polarization nearly 90%, conductivity that is higher by about 2 orders magnitude compared other small molecules, enhanced thermal stability. A plausible explanation these special provided, combined model calculations, supports role electron-electron interaction systems.

Язык: Английский

Процитировано

45
Dynamic Near‐Infrared Circularly Polarized Luminescence Encoded by Transient Supramolecular Chiral Assemblies DOI
Qian Wang,

Hanren Xu,

Zhen Qi

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 13, 2024

Abstract Circularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near‐infrared (NIR) CPL‐active materials, especially those that exhibit high g lum values and can be controlled spatially temporally, rare. Herein, dynamic NIR‐CPL with a value of 2.5×10 −2 was achieved through supramolecular coassembly energy‐transfer strategies. The chiral assemblies formed by between adenosine triphosphate (ATP) pyrene derivative exhibited red signal ( 10 −3 ). further introduction sulfo‐cyanine5 resulted process, which not only led to NIR but also increased . Temporal control these realized introducing alkaline phosphatase fabricate biomimetic enzyme‐catalyzed network, allowing turned on. Based on enzyme‐regulated temporally controllable assemblies, multilevel information encryption system developed. This study provides pioneering example construction materials ability perform temporal via assembly strategy, expected aid design complex more closely resemble natural biological systems.

Язык: Английский

Процитировано

18