Thermally Activated Fluorescence vs Long Persistent Luminescence in ESIPT-Attributed Coordination Polymer DOI

Peng‐Yan Fu,

Baoning Li,

Qiang‐Sheng Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2726 - 2734

Опубликована: Янв. 10, 2022

Excited-state intramolecular proton transfer (ESIPT) molecules demonstrating specific enol-keto tautomerism and the related photoluminescence (PL) switch have wide applications in displaying, sensing, imaging, lasing, etc. However, an ESIPT-attributed coordination polymer showing alternative PL between thermally activated fluorescence (TAF) long persistent luminescence (LPL) has never been explored. Herein, we report assembly of a dynamic Cd(II) (LIFM-101) from ESIPT-type ligand, HPI2C (5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic acid). For first time, TAF and/or color-tuned LPL can be achieved by controlling temperature under guidance ESIPT excited states. Noteworthily, twisted structure ligand LIFM-101 achieves effective mixture higher-energy states, leading to ISC (intersystem crossing)/RISC (reverse intersystem crossing) energy high-lying keto-triplet state (Tn(K*)) singlet (S1(K*)). Meanwhile, experimental theoretical results manifest occurrence probability relevance among RISC, ISC, internal conversion (IC) this unique polymer, unprecedented TAF/LPL switching mechanism, paving way for future design application advanced optical materials.

Язык: Английский

Encyclopedia of Analytical Chemistry DOI
Freek Ariese, Khokan Roy,

Ravi Kumar

и другие.

Wiley eBooks, Год журнала: 2006, Номер unknown

Опубликована: Сен. 11, 2006

Язык: Английский

Процитировано

7136

Small molecule-based ratiometric fluorescence probes for cations, anions, and biomolecules DOI

Min Hee Lee,

Jong Seung Kim, Jonathan L. Sessler

и другие.

Chemical Society Reviews, Год журнала: 2014, Номер 44(13), С. 4185 - 4191

Опубликована: Окт. 6, 2014

Quantitative determination of specific analytes is essential for a variety applications ranging from life sciences to environmental monitoring.

Язык: Английский

Процитировано

1524

Solvatochromic and Fluorogenic Dyes as Environment-Sensitive Probes: Design and Biological Applications DOI
Andrey S. Klymchenko

Accounts of Chemical Research, Год журнала: 2017, Номер 50(2), С. 366 - 375

Опубликована: Янв. 9, 2017

ConspectusFluorescent environment-sensitive probes are specially designed dyes that change their fluorescence intensity (fluorogenic dyes) or color (e.g., solvatochromic in response to microenvironment polarity, viscosity, and molecular order. The studies of the past decade, including those our group, have shown these molecules become universal tools sensing imaging. In fact, any biomolecular interaction organization results modification local microenvironment, which can be directly monitored by types probes. this Account, main examples summarized according design concepts. Solvatochromic constitute a large class polarity. Generally, they push–pull undergoing intramolecular charge transfer. Emission highly polarized excited state shifts red more polar solvents. Excited-state proton transfer is second key concept efficient dyes, respond changing relative two emissive tautomeric forms. Due sensitivity polarity hydration, been successfully applied biological membranes for studying lipid domains (rafts), apoptosis endocytosis. As fluorescent labels, detect practically type interactions, involving proteins, nucleic acids biomembranes, because binding event excludes water from site. On other hand, fluorogenic usually exploit rotation (conformation change) as concept, with rotors being representatives. These were particularly imaging viscosity order biomembranes well light up targets, such antibodies, aptamers receptors. emerging concepts achieve include ground-state isomerization, aggregation-caused quenching, aggregation-induced emission. isomerization exploits, instance, polarity-dependent spiro-lactone formation silica-rhodamines. quenching uses disruption self-quenched dimers nanoassemblies less environments biomolecules. emission couples target recognition dye aggregates. Overall, enable background-free bioimaging wash-free conditions quantitative analysis when combined advanced microscopy, lifetime (FLIM) ratiometric Further development should address some remaining problems: (i) improving optical properties, especially brightness, photostability, far-red near-infrared operating range; (ii) minimizing nonspecific interactions systems; (iii) adaptation microscopies, notably superresolution vivo

Язык: Английский

Процитировано

1012

Excited-state intramolecular proton-transfer (ESIPT)-inspired solid state emitters DOI

Vikas S. Padalkar,

Shu Seki

Chemical Society Reviews, Год журнала: 2015, Номер 45(1), С. 169 - 202

Опубликована: Окт. 27, 2015

The state-of-the-art of ESIPT-inspired solid state emitters and their photophysical properties applications in recent 5 years were systematically reviewed.

Язык: Английский

Процитировано

928

Unraveling the Detailed Mechanism of Excited-State Proton Transfer DOI
Panwang Zhou, Keli Han

Accounts of Chemical Research, Год журнала: 2018, Номер 51(7), С. 1681 - 1690

Опубликована: Июнь 15, 2018

ConspectusAs one of the most fundamental processes, excited-state proton transfer (ESPT) plays a major role in both chemical and biological systems. In past several decades, experimental theoretical studies on ESPT systems have attracted considerable attention because their tremendous potential fluorescent probes, imaging, white-light-emitting materials, organic optoelectronic materials. is related to fluorescence properties usually occurs an ultrafast time scale at or below 100 fs. Consequently, steady-state femtosecond time-resolved absorption, fluorescence, vibrational spectra been used explore mechanism ESPT. However, based previous studies, direct information, such as transition state geometries, energy barrier, surface (PES) reaction, difficult obtain. These data are important for unravelling detailed reaction can be obtained from state-of-the-art ab initio calculations.In recent years, increasing number led progress. This Account presents advances mainly those our group. We focus cases where great importance indispensable, resolving debate stepwise concerted double (ESDPT), revealing sensing chemosensors, illustrating effect intermolecular hydrogen bonding intramolecular (ESIPT) investigating quenching by twisting process, determining size solute·(solvent)n cluster solvent-assisted reaction. Through calculation vertical excitation energies, optimization construction PES reactions, we provide modifications experimentally proposed mechanisms completely new mechanism. Our inspirational successfully explain results; some further confirmed provided guidance researchers design chemosensors.Determination barrier accurate key with methods. approach becomes complicated when charge involved time-dependent density functional theory (TDDFT) method optimally tuned range-separated TDDFT provides alternative way. To unveil driving force molecular dynamics combined intrinsic coordinate calculations employed. advanced approaches should

Язык: Английский

Процитировано

513

Fluorescent Probes for Lipid Rafts: From Model Membranes to Living Cells DOI
Andrey S. Klymchenko,

Rémy Kreder

Chemistry & Biology, Год журнала: 2013, Номер 21(1), С. 97 - 113

Опубликована: Дек. 19, 2013

Язык: Английский

Процитировано

482

Metal–Organic Frameworks with Multiple Luminescence Emissions: Designs and Applications DOI
Hua‐Qing Yin, Xue‐Bo Yin

Accounts of Chemical Research, Год журнала: 2020, Номер 53(2), С. 485 - 495

Опубликована: Янв. 30, 2020

ConspectusEmissive species are powerful for luminescent detection with high sensitivity and simple procedure light-emitting diode (LED) lighting because of their efficiency, long lifetime, low energy consumption. Here we propose the concept multiple luminescence emissions from a single matrix or under single-wavelength excitation. Multiemission not only realizes sensing but also possesses capacity self-reference environment-free interferences. The color change is convenient visible detection. In multiemission species, every emissive center responds to specific analyte improve efficiency multiple-target extends applications anticounterfeiting, colorful LEDs, information storage. To date, it still challenging combine more than one type in species. Obtaining excitation needs exquisite design.Metal–organic frameworks (MOFs) porous hybrid assemblies prepared metal ions organic ligands. Metal nodes ligands large π-conjugated systems have potential construction MOFs. Abundant diverse precursors provide possibility prepare MOFs emissions. pores channels act as hosts encapsulate guest additional sites.In this Account, multiple-luminescence (ML-MOFs) summarize recent research progress on designs, constructions, reported by our group others. ML-MOFs that possess Six different kinds strategies introduced: (1) both MOFs; (2) use mixed-metal centers (3) combination whole achieve application; (4) host–guest after encapsulation species; (5) organization MOF multiemission; (6) exhibiting dual emission ML-MOFs. We discuss mechanisms realize excitation, such antenna effect excited-state intramolecular proton transfer. ratiometric sensing, LED lighting, storage summarized. With hope spark new ideas inspire endeavors design ML-MOFs, especially postsynthetic techniques modification, exchange, deprotection, promote storage,

Язык: Английский

Процитировано

445

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution DOI Creative Commons
Tatu Kumpulainen, Bernhard Lang, Arnulf Rosspeintner

и другие.

Chemical Reviews, Год журнала: 2016, Номер 117(16), С. 10826 - 10939

Опубликована: Дек. 13, 2016

Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of optically populated excited state. This involves relaxation intramolecular and/or solvent modes. As a consequence, reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend excitation wavelength contrary slower processes occurring from equilibrated states. Such ultrafast photoinduced do obey Kasha–Vavilov rule. Nonequilibrium effects also observed diffusion-controlled intermolecular directly after photoexcitation, their proper description gives access intrinsic that normally hidden diffusion. Here we discuss these topics relation organic homogeneous liquids. Discussed include intra- electron- proton-transfer processes, as well photochromic with without bond breaking formation, namely ring-opening cis–trans isomerizations, respectively.

Язык: Английский

Процитировано

381

Breaking the Kasha Rule for More Efficient Photochemistry DOI
Alexander P. Demchenko, В. И. Томин, Pi‐Tai Chou

и другие.

Chemical Reviews, Год журнала: 2017, Номер 117(21), С. 13353 - 13381

Опубликована: Окт. 9, 2017

This paper provides a systematic review and analysis of different phenomena that violate basic principle, Kasha's rule, when applied to photochemical reactions. In contrast the classical route ultrafast transition lowest energy excited state reaction starting therein, in some cases, these reactions proceed directly from high-energy states. Nowadays, this phenomenon can be observed for number major types excited-state reactions: harvesting product via intersystem crossing; photoisomerizations; bond-breaking; electron, proton, transfers. We show specific conditions their observation are determined by kinetic factors. They should among fastest studied systems, competing with vibrational relaxation radiative or nonradiative processes occurring upper The anti-Kasha effects, which provide an important element sheds light on mechanisms transformations, open new possibilities selective control variety practical applications. Efficient utilization excess electronic enhance performance systems artificial photosynthesis photovoltaic devices. modulation reporting signal excitation lead technologies optical sensing imaging.

Язык: Английский

Процитировано

378

Excited-State Conformational/Electronic Responses of Saddle-ShapedN,N′-Disubstituted-Dihydrodibenzo[a,c]phenazines: Wide-Tuning Emission from Red to Deep Blue and White Light Combination DOI
Zhiyun Zhang,

Yu-Sin Wu,

Kuo‐Chun Tang

и другие.

Journal of the American Chemical Society, Год журнала: 2015, Номер 137(26), С. 8509 - 8520

Опубликована: Июнь 15, 2015

A tailored strategy is utilized to modify 5,10-dimethylphenazine (DMP) donor-acceptor type N,N'-disubstituted-dihydrodibenzo[a,c]phenazines. The representative compounds DMAC (N,N'-dimethyl), DPAC (N,N'-diphenyl), and FlPAC (N-phenyl-N'-fluorenyl) reveal significant nonplanar distortions (i.e., a saddle shape) remarkably large Stokes-shifted emission independent of the solvent polarity. For with higher steric hindrance on N,N'-substituents, normal also appears, for which peak wavelength reveals solvent-polarity dependence. These unique photophysical behaviors are rationalized by electronic configuration coupled conformation changes en route geometry planarization in excited state. This proposed mechanism different from symmetry rule imposed explain anomalously long-wavelength DMP firmly supported polarity-, viscosity-, temperature-dependent steady-state nanosecond time-resolved spectroscopy. Together femtosecond early dynamics computational simulation reaction energy surfaces, results lead us establish sequential, three-step kinetics. Upon excitation N,N'-disubstituted-dihydrodibenzo[a,c]phenazines, intramolecular charge-transfer takes place, followed combination polarization stabilization skeletal motion toward planarization, i.e., elongation π-delocalization over benzo[a,c]phenazines moiety. Along encounter raised N,N'-disubstitutes, resulting local minimum state, intermediate. initial intermediate, final state renders full spectrum interest significance their anomalous photophysics. Depending rigidity, N,N'-disubstituted-dihydrodibenzo[a,c]phenazines exhibit multiple emissions, can be widely tuned red deep blue even white light generation upon optimization surrounding media.

Язык: Английский

Процитировано

304