A Photoswitchable and Photoluminescent Organic Semiconductor Based On Cation–π and Carboxylate–Pyridinium Interactions: A Supramolecular Approach

Roy, Sandipan; Mondal, Sankar Prasad; Ray, S. K.; Biradha, Kumar

doi:10.1002/anie.201205822

Cited by 68 publications

(52 citation statements)

References 45 publications

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“…[10a] Phase purity of single-crystal samples for all tests was previously checked by elemental analyses,p owder X-ray diffraction (PXRD), and infrared (IR) (see the Experimental Section and Figure S1 in the Supporting Information). [8,11] Thep ercentage contributions of primary intermolecular interactions were 52.1 %a nd 17.9 %f or O···H hydrogen bond and p-stacking, respectively (Supporting Information, Figure S3). The molecular structure of 1 contains one isolated (H 2 bipy) 2+ cation, and two (Hox) À anion.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[6] If the back reaction can occur thermally,t he phenomenon is called T-type photochromism. 16 times), [8] and represents arecord for photoswitchable organic semiconductors.Using the colored form (1B), we successfully realized the dropping of conductivity at high temperatures for the first time.Compound 1 was synthesized by the reported procedure. [9] That is to say,a ts uitable high temperature,v iologen-based semiconductors will undergo reverse ET reactions and thus result in ad rop of conductivity.T herefore,v iologen-based photochromic semiconductors should be excellent models to realize the breaking of intrinsic positive relation between conductance and temperature.…”

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confidence: 99%

“…16 times), [8] and represents arecord for photoswitchable organic semiconductors.Using the colored form (1B), we successfully realized the dropping of conductivity at high temperatures for the first time. 16 times), [8] and represents arecord for photoswitchable organic semiconductors.Using the colored form (1B), we successfully realized the dropping of conductivity at high temperatures for the first time.…”

mentioning

confidence: 99%

“…Both thermogravimetric analysis (Supporting Information, Figure S2) and PXRD data (Supporting Information, Figure S1) show that 1 is thermally stable at least up to 180 8 8C. [8,11] Thep ercentage contributions of primary intermolecular interactions were 52.1 %a nd 17.9 %f or O···H hydrogen bond and p-stacking, respectively (Supporting Information, Figure S3). Here,t he Hirshfeld surfaces and the associated 2D-fingerprint of (H 2 bipy) 2+ were employed to show the intermolecular interactions.…”

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confidence: 99%

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A Smart Photochromic Semiconductor: Breaking the Intrinsic Positive Relation Between Conductance and Temperature

Sun

Wang

et al. 2019

Angew Chem Int Ed

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Breaking the intrinsic rule of semiconductors that conductivity increases with increase of temperature and realizing adramatic dropping of conductivity at high temperature may arouse new intriguing applications,s uch as circuit overload or over-temperature protecting. This goal has now been achieved through T-type electron-transfer photochromism of one organic semiconductor assembled by intermolecular cation···p interactions.C onductivity of the viologen-based model semiconductor (H 2 bipy)(Hox) 2 (H 2 bipy = 4,4'-bipyridin-1,1'-dium;o x= oxalate) increased by 2o rders of magnitude after photoinduced electron transfer (a recordf or photoswitchable organic semiconductors) and generation of radical cation···p interactions,a nd fell by approximately 81 %a t 100 8 8Ct hrough reverse electron transfer and degeneration of the radical cation···p interactions.T he model semiconductor has at least two different electron transfer pathwaysi nt he decoloration process.The development of electronic industry depends largely on the design and synthesis of new semiconductors.For instance, perovskites have brought appealing applications for solar cells, [1] photodetectors, [2] radiation detectors, [3] and X-ray imagers in recent years. [4] Some important applications of semiconductors are strongly related to their intrinsic properties.F or instance,the intrinsic characteristic that conductivity (s)i ncreases with the rise of temperature has been used to fabricate thermistors,w hich are widely used in production, life,medical, research, teaching,and so on. If conductivity has as udden drop at high temperature,i ntriguing applications will be developed. Fore xample,t he corresponding semiconductor can act as ac ircuit protector in the cases such as circuit overload, short circuit, or appearance of an external heat source.This work presents an effective strategy to realize this goal.Photochromic materials can reversibly convert between two stable forms with different electronic and molecular structures, [5] and thus find many appealing applications. [6] If the back reaction can occur thermally,t he phenomenon is called T-type photochromism. [5] As illustrated in Figure 1, if conductivity of one T-type photochromic semiconductor increases after photoconversion from A to B (coloration process), then the heat-induced reverse reaction from B' ' to A' ' (decoloration process) will cause the dropping of conductivity and realize the breaking of intrinsic positive relation between conductance and temperature at high temperature.V iologen (N,N'-disubstituted-bipyridinium) compounds are famous owing to their electron-transfer (ET) photochromic properties.W e [7] and the Roy group [8] recently reported that viologen-based semiconductors could be obtained through infinite stacking of viologen components by cation···p interactions,a nd they showed ar emarkable increase of conductivity after photoinduced electron transfer (PIET) from an electron donor to the viologen p-aggregate and generation of radical cation···p interactions.Decoloration of vi...

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Section: Angewandte Chemiementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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A Smart Photochromic Semiconductor: Breaking the Intrinsic Positive Relation Between Conductance and Temperature

Sun

Wang

et al. 2019

Angew Chem Int Ed

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“…On the contrary, all the polymers emit the visible light upon the UV excitation (see Figure for the photoluminescence emission spectra of the polymers). The emission of the polymers can originate from the excitation of the partly conjugated polymer chains of polyacetylene type and/or the transition of the CT complex N ‐benzylpyridinium/Br − …”

Section: Resultsmentioning

confidence: 77%

Ionic π‐Conjugated Polyelectrolytes by Catalyst Free Polymerization of Bis(pyridyl)acetylenes and Bis[(pyridyl)ethynyl]benzenes

Faukner

Trhlíková

Zednı́k

et al. 2015

Macro Chemistry & Physics

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The spontaneous, catalyst free polymerization of four monomers of the bis(pyridyl)acetylene and bis[(pyridyl)ethynyl]benzene types containing either 2-pyridyl or 4-pyridyl groups via activation with benzyl bromide leads to ionic π-conjugated polyacetylene-type polyelectrolytes (CPEs). All polymers are characterized by means of NMR, IR, UV/vis and photoluminescence spectroscopies, thermogravimetric analysis (TGA) and matrix assisted laser desorption/ ionization time of fl ight mass spectrometry (MALDI-TOF MS). The position of the pyridyl groups in the monomer infl uences the degree of quaternization and the extent of conjugation of CPEs. Monomers with 4-pyridyl groups provide CPEs with a low extent of quaternization [N + /(N + + N) = 0.27-0.34] and high extent of conjugation. On the other hand, the CPEs derived from 2-pyridyl-containing monomers are highly quaternized [N + /(N + + N) = 0.77-1.00], however, possess lower conjugation of the main chains. The mechanism assuming quaternization and polymerization as competitive reactions is proposed to explain the difference in the extent of quaternization of CPEs. Prepared CPEs i) are well soluble in polar solvents, e.g., water, methanol, dimethyl sulfoxide, and dimethylformamide, ii) exhibit photoluminescence (emission in the violet to yellow region), and iii) possess high thermal stability. materials with a wide variety of applications, [1][2][3][4][5][6][7][8] including light-emitting diodes (LEDs), [ 9 ] light-emitting electrochemical cells (LECs), [ 10 ] plastic lasers, [ 11 ] solar cells, [ 12 ] fi eld-effect transistors (FETs) [ 13 ] and porous materials. [ 14,15 ] The π-conjugated polyelectrolytes (CPEs) represent a special subclass of CPs. [ 16 ] The CPE polymers comprise π-conjugated main chains and ionic and/or ionizable groups. Unlike the majority of neutral CPs, CPEs additionally exhibit i) solubility in polar solvents as water, aqueous solutions, alcohols, and others environmentally friendly solvents, [17][18][19] ii) amphiphilic nature, which gives CPE macromolecules capability of self-assembling in solutions and ability to interact specifi cally with particular species under measurable optical and/or electrical responses, and iii) simultaneous electronic and ionic conductivity [ 20 ] reducing the electron-injection barrier Emission spectra 400 450 500 550 600 650 Wavelength (nm) Br N N N N N N N N N N Br Br Br Br Br NO CATALYST poly(4PD)

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Relationship Between Structure and Electroluminescent, Photochromic, or Second‐Order Nonlinear Optical Property

Wang

Zhao

Wang

et al. 2021

Advanced Structural Chemistry

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A Photoswitchable and Photoluminescent Organic Semiconductor Based On Cation–π and Carboxylate–Pyridinium Interactions: A Supramolecular Approach

Cited by 68 publications

References 45 publications

A Smart Photochromic Semiconductor: Breaking the Intrinsic Positive Relation Between Conductance and Temperature

A Smart Photochromic Semiconductor: Breaking the Intrinsic Positive Relation Between Conductance and Temperature

Ionic π‐Conjugated Polyelectrolytes by Catalyst Free Polymerization of Bis(pyridyl)acetylenes and Bis[(pyridyl)ethynyl]benzenes

Relationship Between Structure and Electroluminescent, Photochromic, or Second‐Order Nonlinear Optical Property

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