Spiropyrans and spirooxazines

Voloshin, N. A.; Chernyshev, A. V.; Bezuglyi, S. O.; Метелица, А. В.; Voloshina, E. N.

doi:10.1007/s11172-008-0022-y

Cited by 19 publications

(9 citation statements)

References 20 publications

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“…The following points in particular summarize the necessity of the thin film MOFs in order to achieve maximized photoresponse in MOF‐based material toward future advanced applications: (1)While the molar absorption coefficient of azobenzene is in the range of 10 4 m −1 cm −1 , the molar absorption coefficient of spiropyran and merocyanine is typically dramatically larger, resulting in light penetration depths of 1 μm or below. Thus, for particulate forms of MOFs, e.g., in pellets or drop‐cast powder suspensions, only the chromophores in the outer surface region of the sintered MOF material can be reached.…”

Section: Discussionmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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In recent years, a particularly attractive and novel strategy has become available for the fabrication of photoresponsive, porous, and crystalline molecular solids from appropriately functionalized chromophoric linkers. The crystallinity of these materials allows a rather straightforward description and analysis using theoretical methods, thus tremendously accelerating the design of novel materials. This new class of crystalline molecular solids is referred to as metal-organic frameworks, MOFs (or porous coordination polymers, PCPs). [1] MOFs are constructed from metal-/metal-oxo nodes and organic linkers (Figure 1). The incorporation of photoactive species into MOFs may be realized by using them as linkers (method L) or attaching them to a linker (method A), as shown in Figure 1a. In addition, the porosity of MOFs allows the loading of chromophoric compounds as guests (method G) into the pores of this interesting framework material.In this review article, we mainly focus on organic photoactive species, which are either simply loaded as guests into porous MOFs or used after appropriate functionalization as building blocks for the construction of the framework (methods L, A, and G). [2] It is important to note that in the context of photoresponsive behavior, MOFs carry a potential which by far exceeds that of nonporous coordination polymers. This is because simple loading of guest/solvent molecules of different size/polarity/functionality in the MOF pores can impart a large optical response, which is useful, e.g., for sensing applications. [3] As an example, the solvent-dependent optical response or solvatochromism [4] is illustrated in Figure 1b. Such effects cannot be realized for nonporous coordination polymers.The different types of photoresponsive molecules addressed in this review can be grouped into two classes. The first contains molecules where the structure remains essentially unchanged upon light-induced electronic excitation, and the second contains molecular species that change their structure or conformation upon absorption of photons (molecular switches).Light with a wavelength in the range 200-800 nm (6.2-1.5 eV) can excite a molecule to a transient excited electronic state. The transient state then decays to a low-energy state, either the parent ground state or another longer-lived excited state. Decay time scales are in the range 10 −12 -10 1 s, and the released energy can be radiative or nonradiative in nature. For many applications, nonradiative energy loss is unwanted, When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal-organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coo...

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Section: Discussionmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…In the absence of additional ligation sites except the phenolate oxygen atom, the complex binding constants are rather weak and light induced ring-closure results in the expulsion of the metal ion. , However, the stability of the complex can be significantly increased by using a second ligand besides MC for complexation. Different stoichiometries depending on the metal (M) and the SP substitution have been described, most of them belonging either to an MC/M ratio of 2/1 or 1/1. − Irradiation of the MC–M complexes with light was postulated to result in the expulsion of the metal ion and reformation of the SP structure, as well as a cis ⇌ trans isomerization of the central MC double bond, while maintaining the coordination toward the metal center …”

Section: Introductionmentioning

confidence: 99%

Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR

et al. 2019

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As one of the best studied photoswitches, spiropyrans (SPs) have attracted significant interest in the scientific community. Among the many stimuli to alter the isomerization into the merocyanine (MC) isomer, such as temperature, pH, solvent polarity, redox potential, or mechanical force, the ability of the MC form to act as a ligand site for metal complexation has recently raised new attention. We herein synthesize hitherto undescribed coordination compounds of 8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro-[chromene-2,2′-indoline] with s-block ([Ca(MC)4](ClO4)2), d-block ([Zn(MC)2(MeCN)2](ClO4)2, [Ni(MC)2(MeCN)2](ClO4)2), as well as f-block ([La(NO3)3(MC)2]) metals. All complexes are structurally described by X-ray crystallography and systematically investigated in solution via Job’s method of continuous variations (Job plots), as well as online NMR spectroscopic kinetic experiments with in situ irradiation of the analyte solution inside the NMR spectrometer (LED-NMR). We can unambiguously identify the photoresponsive nature of the complexes in solution, which is a crucial step toward the application of these promising molecules in material science.

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“…Benzindole 4 was obtained by the decarboxylation of acid 3. 2 (5 Methoxy 1,2 di methyl 1H benzo[g]indol 3 yl)oxoacetyl chloride (5) was formed due to the acylation of compound 4 with oxalyl chloride, and the reaction of acid chloride 5 with 3 thienylacetic acid affords, similarly to the synthesis of indolemaleic anhydrides, 10 3 (5 methoxy 1,2 dimethyl 1H benzo[g]indol 3 yl) 4 (3 thienyl)furan 2,5 dione (6). The reaction of furandione 6 with alkyl and aryl amines gives 1 alkyl and 1 aryl 3 (5 methoxy 1,2 di methyl 1H benzo[g]indol 3 yl) 4 (3 thienyl) 1(H)pyr role 2,5 diones 7a-d (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…4, 6 Fluo rescence of one of the isomeric forms provides possibili ties for optical information recording and creation of mo lecular switches with the fluorescent signal function. [5][6][7] Many dihetarylethenes with various heterocyclic substitu ents, such as thiophene, benzothiophene, furan, benzo furan, thiazole, indole, pyrazole, and pyrrole moieties, have been synthesized to the present time. In the most part of cases, these are symmetric systems.…”

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confidence: 99%

Synthesis and photochromic properties of novel nonsymmetric dihetarylethenes based on benzindole and thiophene

et al. 2010

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ul. Chekhova, 344006 Rostov on Don, Russian FederationNovel nonsymmetric dihetarylethenes 3 (5 methoxy 1,2 dimethyl 1H benzo[g]indol 3 yl) 4 (3 thienyl) furan 2,5 dione and 1 alkyl and 1 aryl 3 (5 methoxy 1,2 dimethyl 1H benzo[g]indol 3 yl 4 (3 thienyl) 1(H) pyrrole 2,5 diones were synthesized. The substitution of the furandione moiety for pyrroledione gives rise to the radiation and photochemical channels of deactivation of the electron excitation energy of dihetarylethenes. The products of photolysis of pyrrolediones undergo recyclization in both the ground and excited states.

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Spiropyrans and spirooxazines

Cited by 19 publications

References 20 publications

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR

Synthesis and photochromic properties of novel nonsymmetric dihetarylethenes based on benzindole and thiophene

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