Multistimuli Two-Color Luminescence Switching via Different Slip-Stacking of Highly Fluorescent Molecular Sheets

Yoon, Seong Jun; Chung, Jong Won; Gierschner, Johannes; Kim, Kil Suk; Choi, Moon Gun; Kim, Dongho; Park, Soo Young

doi:10.1021/ja1044665

Cited by 900 publications

(562 citation statements)

References 61 publications

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“…Mechanochromic materials show changes in emission colour in the presence of mechanical stimuli (for example, shearing, grinding and rubbing) because of the interruption of intermolecular interactions (for example, p-p stacking and hydrogen bonds) [6][7][8][9][10] . Vapochromic luminescence has been observed in materials that are responsive to volatile organic compounds 11,12 . Electric field is an important external stimulus.…”

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confidence: 99%

Smart responsive phosphorescent materials for data recording and security protection

et al. 2014

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Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection. D ata recording, storage and security technologies have been widely utilized in economic and military fields as well as in our daily life. Smart luminescent materials that are responsive to external stimuli have received considerable attention in the construction of optical data recording and storage devices [1][2][3][4][5] . These materials have been classified on the basis of the types of external stimuli that they are responsive to. Mechanochromic materials show changes in emission colour in the presence of mechanical stimuli (for example, shearing, grinding and rubbing) because of the interruption of intermolecular interactions (for example, p-p stacking and hydrogen bonds) [6][7][8][9][10] . Vapochromic luminescence has been observed in materials that are responsive to volatile organic compounds 11,12 . Electric field is an important external stimulus. Electrochromism occurs in p-conjugated polymers because of the reversible transition between two redox states [13][14][15][16] . However, materials showing electrochromic luminescence, which is distinct luminescence colour responses to an electric field, are scarce. We envision the potential commercial applications of electrochromic luminescent materials because they can be conveniently integrated into semiconductor-based electronic devices. In addition, it is conceivable that compounds simultaneously showing mechanochromic, vapochromic and electrochromic luminescence are of great use to the development of multifunctional materials.Phosphorescent transition-metal complexes, such as those of Ir(III) and Pt(II), have been extensively studied for various photonic and electronic applications because of their rich excited-state properties, including high luminescence quantum yields, long emission lifetimes, large Stokes shifts, high photostability and various luminescence colours [17][18][19][20] . These complexes have also been utilized a...

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confidence: 99%

Smart responsive phosphorescent materials for data recording and security protection

et al. 2014

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“…Recently, luminescent materials that are responsive to mechanical stimuli have attracted considerable attention because they have the unique ability to tune their molecular, physical or chemical properties via macroscopic stimulation [5][6][7][8] . Several mechanistic explanations for the mechanically stimulated changes in the colour of the luminescence have been proposed: a phase transformation of the solid structure [9][10][11][12][13][14][15][16] , excimer formation or dissolution [17][18][19] and mechanical stress-induced chemical changes 20,21 . However, the development of new materials with luminescent mechanochromism still depends heavily on serendipitous discovery or random screening; studies based on rationally designed luminophoric compounds and sensitivity to mechanical stimuli remains rare.…”

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Design amphiphilic dipolar π-systems for stimuli-responsive luminescent materials using metastable states

et al. 2014

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p-Conjugated compounds that exhibit tunable luminescence in the solid state under external mechanical stimuli have potential applications in sensors and imaging devices. However, no rational designs have been proposed that impart these mechano-responsive luminescent properties to p-conjugated compounds. Here we demonstrate a strategy for mechanoresponsive luminescent materials by imparting amphiphilic and dipolar characteristics to a luminescent p-conjugated system. The oligo(p-phenylenevinylene) luminophore with a didodecylamino group at one end and a tri(ethylene glycol) ester group at the other end yields segregated solid structures by separately aggregating its hydrophobic and hydrophilic moieties. The segregated structures force the molecules to align in the same direction, thereby generating a conflict between the side-chain aggregation and dipolar stabilization of the p-system. Consequently, these metastable solid structures can be transformed through mechanical stimulation to a more stable structure, from a p-p stacked aggregate to a liquid crystal and further to a crystalline phase with variable luminescence.

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“…[25,26] Notably, the planar stacking of the acceptor and conjugated units in these needlelike crystals is appro priate for the conduction of π electrons, [27] which was definitely conformed by the highest occupied molecular orbit (HOMO)-lowest unoccupied molecular orbital (LUMO) orbital analysis of twocoupled neighboring molecules in form D ( Figure S8, Sup porting Information).…”

Section: Wwwadvelectronicmatdementioning

confidence: 78%

Tuning Luminescence and Conductivity through Controlled Growth of Polymorphous Molecular Crystals

Chen

Liu

et al. 2017

Adv Elect Materials

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on the basis of traditional conductive polymers. Over the last couple of decades, however, much progress has been made in the development of optoelectronic devices based on organic small molecules. [8,12] Several archetypical polymorphic mole cular solids are of high interest and utility in optical and electronic applications. [8][9][10][11][12] Previous studies of archetypical polymor phic systems have found that the crystal lization of polymorphs can be affected by many factors, principally the nature of the solvent and the presence of additives. [13,14] These materials have provided great opportunities to explore the fundamentals of polymorphism. [15] Indeed, determining the origins of polymorphism is important for both applied science and our funda mental understanding of crystal packing and structure-property relationships.For organic semiconductors, charge transport between organic molecules is related to the degree of electronic coupling among neighboring molecules as well as the reorganization energy involved during transformations from neutral to charged or charged to neutral states. [16,17] Nevertheless, clear structure-property correlations can be difficult to identify, especially for the same compound in different molecular crystal packing arrangements which can influence the resulting optical and electronic properties. In this study, we have found that different packing styles can lead to single crystals exhibiting dramatically different optical and elec tronic properties. Herein, we describe the synthesis and struc tural characterization of a polymorphic compound (E)2{4[4 (9Hcarbazol9yl)styryl]benzylidene}malononitrile (TCBR) and reveal how its luminescence and electronic properties depend on its modes of packing in the solid state. In particular, we have found that crystals featuring different stacking modes exhibit distinctly different charge transport characteristics. Results and DiscussionThe synthesis of the molecule TCBR is illustrated in Scheme 1. The novel acetalprotected stilbene 1, selected for extension of the π conjugation, was prepared through a Wadsworth-Emmons reaction. Starting from the diethyl phosphonate, the trans stilbene form of 1 was obtained preferentially. Subsequent removal of the acetal group, using trifluoroacetic acid, afforded the desired (E)4[4(9Hcarbazol9yl)styryl]benzaldehyde 2.Clear structure-property correlation is of crucial importance for molecular materials for optical and electronic application. Here, a new intramolecular charge transfer compound (E)-2-{4-[4-(9H-carbazol-9-yl)styryl]benzylidene}-malononitrile (TCBR) with a dicyanovinyl group as the electron acceptor and a carbazole group as the electron donor is designed and synthesized. Four different single crystals based on the cis and trans isomeric forms of this compound are grown simultaneously, which are both kinetically and thermodynamically stable. The different packing modes give rise to a dynamic crystal structure change, leading to dramatically different optical and electronic properties. The closer...

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Multistimuli Two-Color Luminescence Switching via Different Slip-Stacking of Highly Fluorescent Molecular Sheets

Cited by 900 publications

References 61 publications

Smart responsive phosphorescent materials for data recording and security protection

Smart responsive phosphorescent materials for data recording and security protection

Design amphiphilic dipolar π-systems for stimuli-responsive luminescent materials using metastable states

Tuning Luminescence and Conductivity through Controlled Growth of Polymorphous Molecular Crystals

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