Application to Photoreactive Materials of Photochemical Generation of Superbases with High Efficiency Based on Photodecarboxylation Reactions

Arimitsu, Koji; Endo, Ryosuke

doi:10.1021/cm4022485

Cited by 76 publications

(74 citation statements)

References 17 publications

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“…Melting points were measured on an Electrothermal 9200 apparatus. 1 H and 13 C NMR spectra, homonuclear 1 H− 1 H COSY and heteronuclear 1 H− 13 C HETCOR correlation spectroscopy were recorded on a JEOL eclipse ECA +500 spectrometer. Chemical shifts (ppm) are relative to (CH 3 ) 4 Si for 1 H and 13 C. High resolution mass spectra were obtained with an Agilent G1969A spectrometer.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…1,2 On the other hand, Schiff bases are common organic structures which can be easily synthesized through a one-step synthetic procedure. 3,4 As a result, a vast library of Schiff bases has been developed for several applications, including optical data storage, 5−7 molecular electronics and computing, 8,9 molecular switches 10,11 and sensors.…”

Section: ■ Introductionmentioning

confidence: 99%

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Multiresponsive Photo-, Solvato-, Acido-, and Ionochromic Schiff Base Probe

2015

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Nonclassical protomeric tautomerism in Schiff bases have the advantage of controlling and differentiating specific interactions in the −CN− linkage since its interactions are not governed by keto−enol tautomerism.Here, we report about the optical properties of a Schiff base probe (P1). X-ray structure analysis evidenced the existence of an intramolecular hydrogen bond which is responsible of a photochromic-fluorescent behavior. The properties of P1 were investigated by UV−vis and fluorescence spectroscopy in solution and solid state. A positive solvatochromism resulting from specific interactions taking place in P1 was studied by three different solvent scales, namely Lippert−Mataga, Kamlet−Taft, and Catalań, finding consistent results. Moreover, a strong acidochromic behavior was detected and the pK a and pK a * values were determined, finding a photobasic character. Further, an ionochromic behavior was stablished. P1 exhibits a λ-ratiometric fluorescence response toward Sn(IV) giving a luminescence color change from blue to green, displaying also a chromogenic response. Finally, theoretical calculations were conducted to analyze the probe mechanism in terms of natural transition orbitals (NTOs) and spatial extent of charge transfer excitations. The present contribution focused on the factors determining the ability of a single Schiff base probe to present photo-, solvato-, acido-, and ionochromism. ■ INTRODUCTIONOrganic multiresponsive molecules whose optical properties can be regulated by various chemical stimuli have attracted much attention due to their ability to signal different interactions. 1,2 On the other hand, Schiff bases are common organic structures which can be easily synthesized through a one-step synthetic procedure. 3,4 As a result, a vast library of Schiff bases has been developed for several applications, including optical data storage, 5−7 molecular electronics and computing, 8,9 molecular switches 10,11 and sensors. 12,13 However, most of these applications are based on the tautomeric preferences of the Schiff bases, 14 and very few reports regarding specific interactions in nonclassical protomeric tautomerism 15−17 which do not display the typical enolimine−ketoenamine tautomers have been reported. For example, specific interactions in the −CN− imine bond are highly valuable in the field of molecular assembly for micro-and nanostructure fabrication 18 and multiresponsive assemblies. 19−21 In this regard, single small molecules which present multiresponsive properties are highly desirable due to their simplicity to interact with the chemical environment. 22 Further, compared to other covalent bonds such as the click chemistry linkers, the Schiff base structure provides extraordinary reversibility with changing pH values and the stability of these bonds varies with pH, 23−25 or even when changing the polarity and polarizability of the media. 26−28 In addition, Schiff bases having a push−pull character bearing electron acceptor and donor groups connected by a conjugated bridge (D−π−A) ca...

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Multiresponsive Photo-, Solvato-, Acido-, and Ionochromic Schiff Base Probe

2015

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“…Although photosensitive materials based on base-catalyzed reactions have merit in preventing erosion of metallic substrates, PBGs generally have lower quantum yields when compared to PAGs. Recently, in order to improve photosensitivity, some papers regarding PBGs with high quantum yields have been reported, but it has not been yet applied to photopatterning materials [4][5][6][7][8][9]. There is a few report concerning photopatterning materials based on epoxy resins utilizing PBGs.…”

Section: Introductionmentioning

confidence: 99%

Photosensitivity Characteristics of Novel Resists Consisting of a Photobase Generator and an Epoxy Resin

Terada

Furutani

Arimitsu³

2017

J. Photopol. Sci. Technol.

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Most of the photopatterning materials based on epoxy resins are utilizing photoacid generators (PAGs) which generate superacids as catalysts. They have been used for high aspect ratio photoresists in the fabrication of MEMS devices. However, there is a drawback that the acidic species from PAGs will induce metal corrosion. One of the approach to overcome this problem is the use of photobase generators (PBGs) because organic bases would induce no corrosion. Although there is a large number of investigation of PBGs in past time, only few articles have mentioned photoreactive materials relying on PBGs due to its low photosensitivity. We report here highly sensitive photopatterning materials comprising PBG and an epoxy resin bearing carboxylic acid groups. As a result, the photopatterning material showed higher photosensitivity when compared to conventional epoxy resin systems. We obtained high photosensitivity (up to 900 mJ/cm 2 ), high resolution (10 m line and space) patterning materials in thin films of 10 m in thickness.

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“…Alcohols, phenols, carboxylic acids, acid anhydrides, and amines have been examined as hardners [2]. Recently, our group has developed an epoxy resin curing system with a tetrafunctional thiol and photobase generator providing a strong organic base [3]. In this communication, we have focused a unique chemical structure of L-cysteine (Cys) which has thiol and primary amino groups.…”

Section: Introductionmentioning

confidence: 99%