Computational and Crystallographic Examination of Naphthoquinone Based Diarylethene Photochromes

Photochromic compounds have a lengthy history of study and a profusion of applications that stand to gain from these studies. Among the classes of photochromic compounds, diarylethenes show desirable properties including high fatigue resistance and thermal stability, thus meeting some of the most important criteria necessary to enter the realm of practical applications. Recently, photochromic diarylethenes containing quinone functionalities have demonstrated interesting optical and solid-state properties. When properly interfaced with suitable electron withdrawing groups on the aryl component, both the ring-opening and ring-closing reactions can be achieved with visible light; this is in contrast to most other diarylethenes where UV light is required for ring closure. Unfortunately, quantitative conversion from open to closed forms is not possible. In this work, we examine the relative energies of conformations of solid-state structures observed by X-ray crystallography and evaluate their thermal stabilities based on density functional theory (DFT) calculations. Time-dependent DFT (TD–DFT) is used to model the UV-vis absorption spectra of these quinone diarylethenes. We show that spectral overlap between open and closed forms is a major hindrance to full photoconversion.

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Carbonyl Complexes of Iron(II), Ruthenium(II), and Osmium(II) 5,10,15,20-Tetraphenylporphyrinates: A Comparative Investigation by X-ray Crystallography, Solid-State NMR Spectroscopy, and Density Functional Theory

Journal of the American Chemical Society ◽

10.1021/ja9740069 ◽

1998 ◽

Vol 120 (44) ◽

pp. 11323-11334 ◽

Cited By ~ 54

Author(s):

Renzo Salzmann ◽

Christopher J. Ziegler ◽

Nathalie Godbout ◽

Michael T. McMahon ◽

Kenneth S. Suslick ◽

...

Keyword(s):

Density Functional Theory ◽

Solid State ◽

Nmr Spectroscopy ◽

Solid State Nmr ◽

Density Functional ◽

Comparative Investigation ◽

Carbonyl Complexes ◽

Functional Theory ◽

X Ray ◽

X Ray Crystallography

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Structure and photochemical properties of biindenylidene derivatives in the solid state

Journal of Chemical Research ◽

10.3184/030823408x375133 ◽

2008 ◽

Vol 2008 (11) ◽

pp. 647-649

Author(s):

Xu Li ◽

Ping Wang ◽

Jing-jun Liu ◽

Yong-ming Wang ◽

Hai Zhu

Keyword(s):

Solid State ◽

Crystal Structures ◽

Organic Radical ◽

Compound I ◽

X Ray ◽

Photochromic Compounds ◽

X Ray Crystallography ◽

Photochemical Properties ◽

Compound Ii

Two photochromic compounds, trans-3,3′-dipentyl-3,3′-dihydroxy-2,2′-bi-1H-indene-1,1′-dione (I), and cis-3,3′-di (2-methylally)-3,3′-dihydroxy-2,2′-bi-1H-indene-1,1′-dione (II), were synthesised and their crystal structures were determined by X-ray crystallography. The photoinduced properties of the compound were studied. The results showed that compound I exhibited reversible photochromism, and at the same time a stable organic radical was generated, while compound II did not show photochemical properties.

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A Solid-State Fluorescence Switch Based on Triphenylethene-Functionalized Dithienylethene With Aggregation-Induced Emission

Frontiers in Chemistry ◽

10.3389/fchem.2021.665880 ◽

2021 ◽

Vol 9 ◽

Author(s):

Haining Zhang ◽

Xiaoxiao Hu ◽

Huijuan Zhu ◽

Limin Shen ◽

Congmin Liu ◽

...

Keyword(s):

Solid State ◽

Visible Light ◽

Density Functional ◽

Uv Light ◽

Functional Theory ◽

Aggregation Induced Emission ◽

H Nmr ◽

Chemical Structures ◽

Fluorescence Switch ◽

The Density Functional Theory

The development of novel dithienylethene-based fluorescence switches in the aggregated state, and the solid state is highly desirable for potential application in the fields of optoelectronics and photopharmacology. In this contribution, three novel triphenylethene-functionalized dithienylethenes (1–3) have been designed and prepared by appending triphenylethene moieties at one end of dithienylethene unit. Their chemical structures are confirmed by 1H NMR, 13C NMR, and HRMS (ESI). They display good photochromic behaviors with excellent fatigue resistance upon irradiation with UV or visible light in Tetrahydrofuran (THF) solution. Before irradiation with UV light, they exhibit Aggregation Induced Emission (AIE) properties and luminescence behaviors in the solid state. Moreover, upon alternating irradiation with UV/visible light, they display effective fluorescent switching behaviors in the aggregated state and the solid state. The experimental results have been validated by the Density Functional Theory (DFT) calculations. Thus, they can be utilized as novel fluorescence switches integrated in smart, solid-state optoelectronic materials and photopharmacology.

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Research on Photochromic Compounds with Efficient Synthesis and Photochromic Properties of 1-(2-methyl-5-chlorine-3-thienyl)-2-[2-methyl -5-(4-chlorophenyl)-3-thienyl] Perfluorocyclopentene

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.1003.43 ◽

2014 ◽

Vol 1003 ◽

pp. 43-46

Author(s):

Feng Xia Sun ◽

Shi Qiang Cui ◽

Shou Zhi Pu

Keyword(s):

Solid State ◽

Phenyl Ring ◽

Uv Light ◽

Amorphous Film ◽

Fluorescence Properties ◽

Efficient Synthesis ◽

Photochromic Properties ◽

Photochromic Compounds ◽

Fluorescence Switching

A novel unsymmetrical diarylethene derivative bearing both phenyl and thiophene moieties, in which two chlorine groups were separately substituted at thiophene and the para-positions of the terminal phenyl ring, were synthesized. Its photochemical , fluorescence properties were investigated systematically both in solution and PMMA amorphous film. The results showed that this compound exhibited reversible photochromism, changing from colorless to purple after irradiation with 313 UV light both in solution and in PMMA amorphous film. Also, it exhibited remarkable fluorescence switching in the solid state.

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Infinitene: A Helically Twisted Figure-Eight [12]Circulene Topoisomer

10.33774/chemrxiv-2021-pcwcc ◽

2021 ◽

Author(s):

Kenichiro Itami ◽

Maciej Krzeszewski ◽

Hideto Ito

Keyword(s):

Density Functional ◽

Crystal Packing ◽

Uv Light ◽

Photophysical Properties ◽

Three Dimensional ◽

Spectroscopic Studies ◽

Molecular Formula ◽

Chiral Hplc ◽

Practical Applications ◽

Benzene Rings

New forms of molecular nanocarbons particularly looped polyarenes adopting various topologies contribute to the fundamental science and practical applications. Here we report on the synthesis of an infinity-shaped polycyclic aromatic hydrocarbon, infinitene 1 (cyclo[c.c.c.c.c.c.e.e.e.e.e.e]dodecakisbenzene) comprising consecutively fused 12-benzene rings forming an enclosed loop with a strain energy of 60.2 kcal·mol-1. Infinitene 1 represents a topoisomer of still-hypothetical [12]circulene, and its scaffold can be formally visualized as the outcome of the “stitching” of two homochiral [6]helicene subunits by their both ends. The synthetic strategy encompasses transformation of a rationally designed dithiacyclophane to cyclophadiene through the Stevens rearrangement and pyrolysis of the corresponding S,S′-bis(oxide) followed by the UV-light mediated twofold photocyclization. The structure of infinitene 1 is a unique hybrid of helicene and circulene with a molecular formula C48H24, which can be regarded as an isomer for kekulene, [6,6]carbon nanobelt ([6,6]CNB), [12]cyclacene, and tetrabenzo[8]circulene as well. Infinitene 1 is a bench-stable yellow solid with green fluorescence, and soluble to common organic solvents. The figure-eight molecular structure of 1 was unambiguously confirmed by X-ray crystallography. The scaffold of 1, reminiscent of a squeezed spring, stem from its enclosed, fully-fused architecture, is significantly compressed as manifested by a remarkably shortened distance (3.152–3.192 Å) between the centroids of two π-π stacked central benzene rings and the closest C···C distance of 2.920 Å. Combined lamellar and herringbone-like crystal packing suggested three-dimensional electronic inter-actions. Fundamental photophysical properties of infinitene 1 were thoroughly elucidated by means of UV-vis absorption and fluorescence spectroscopic studies as well as density functional theory (DFT) calculations. Its configurational stability enabled separation of the corresponding enantiomers (P,P) and (M,M) by a chiral HPLC. Circular dichroism (CD) and circularly polarized luminescence (CPL) measurements revealed that 1 has moderate |gCD| and |gCPL| values.

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Highly Electron-Deficient Pyridinium-Nitrones for Rapid and Tunable Inverse-Electron-Demand Strain-Promoted Alkyne-Nitrone Cycloaddition to Bicyclo[6.1.0]nonyne

10.26434/chemrxiv.8251370 ◽

2019 ◽

Author(s):

Praveen Gunawardene ◽

Wilson Luo ◽

Alexander M. Polgar ◽

John F. Corrigan ◽

Mark Workentin

Keyword(s):

Density Functional Theory ◽

Reaction Kinetics ◽

Density Functional ◽

Functional Theory ◽

X Ray ◽

Inverse Electron Demand ◽

X Ray Crystallography ◽

Electron Demand

<div> <div> <p>Highly accelerated inverse-electron-demand strain-promoted alkyne-nitrone cycloaddition (IED SPANC) between a sta- ble cyclooctyne (bicyclo[6.1.0]nonyne (BCN)) and nitrones delocalized into a Cα-pyridinium functionality is reported, with the most electron-deficient “pyridinium-nitrone” displaying among the most rapid cycloadditions to BCN that is currently reported. Density functional theory (DFT) and X-ray crystallography are explored to rationalize the effects of N- and Cα-substituent modifications at the nitrone on IED SPANC reaction kinetics and the overall rapid reactivity of pyridinium-delocalized nitrones.</p> </div> </div>

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Operando Visualization of Morphological Dynamics in All-Solid-State Batteries

10.26434/chemrxiv.8299406 ◽

2019 ◽

Author(s):

Xiaohan Wu ◽

Juliette Billaud ◽

Iwan Jerjen ◽

Federica Marone ◽

Yuya Ishihara ◽

...

Keyword(s):

Solid State ◽

Solid Electrolytes ◽

Rational Design ◽

Morphological Evolution ◽

Active Material ◽

Composite Layer ◽

Transference Number ◽

Thermal Stabilities ◽

Solid State Batteries ◽

All Solid State Batteries

<div> <div> <div> <p>All-solid-state batteries are considered as attractive options for next-generation energy storage owing to the favourable properties (unit transference number and thermal stabilities) of solid electrolytes. However, there are also serious concerns about mechanical deformation of solid electrolytes leading to the degradation of the battery performance. Therefore, understanding the mechanism underlying the electro-mechanical properties in SSBs are essentially important. Here, we show three-dimensional and time-resolved measurements of an all-solid-state cell using synchrotron radiation x-ray tomographic microscopy. We could clearly observe the gradient of the electrochemical reaction and the morphological evolution in the composite layer. Volume expansion/compression of the active material (Sn) was strongly oriented along the thickness of the electrode. While this results in significant deformation (cracking) in the solid electrolyte region, we also find organized cracking patterns depending on the particle size and their arrangements. This study based on operando visualization therefore opens the door towards rational design of particles and electrode morphology for all-solid-state batteries. </p> </div> </div> </div>

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A Short History of Navy VLF Solid-State Transmitter Development

10.21236/ada390369 ◽

2001 ◽

Author(s):

R. E. Hammond

Keyword(s):

Solid State ◽

Short History ◽

History Of

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The Structure and Photochromism of 2,4,4,6-Tetraphenyl-4H-thiopyran

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19921326 ◽

1992 ◽

Vol 57 (6) ◽

pp. 1326-1334 ◽

Cited By ~ 11

Author(s):

Jaroslav Vojtěchovský ◽

Jindřich Hašek ◽

Stanislav Nešpůrek ◽

Mojmír Adamec

Keyword(s):

Solid State ◽

Uv Light ◽

Order Reaction ◽

Boat Conformation ◽

X Rays ◽

Exponential Time ◽

First Order ◽

Double Plane ◽

The Mean ◽

Independent Molecules

2,4,4,6-Tetraphenyl-4H-thiopyran, C29H22S, orthorhombic, Pna21, a = 17.980(4), b = 6.956(2), c = 34.562(11) Å, V = 4323(2) Å3, Z = 8, Dx = 1.237 g cm-3, F(000) = 1696, λ(CuKα) = 1.54184 A, μ = 1.372 mm-2, T = 294 K. The final R was 0.050 for the unique set of 3103 observed reflections. The central 4H-thiopyran ring forms a boat conformation for both symmetrically independent molecules with average boat angles 4.4(3) and 6.8(3)° at S and C(sp3), respectively. The mean planes of phenyls at the position 2 and 6 are turned from the double plane of 4H-thiopyran by 42.5(5) and 35.8(3)°, respectively. The investigated material undergoes a photochromic change in the solid state after irradiation with UV light or X-rays. The maximum of the new absorption band is situated at 564 nm. The non-exponential time dependence of photochromic bleaching is analysed in terms of a dispersive first-order reaction.

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