Effect of intramolecular charge transfer on fluorescence and singlet oxygen production of phthalocyanine analogues

Intramolecular charge transfer (ICT) was studied on a series of magnesium, metal-free and zinc complexes of unsymmetrical tetrapyrazinoporphyrazines and tribenzopyrazinoporphyrazines bearing two dialkylamino substituents (donors) and six alkylsulfanyl or aryloxy substituents (non-donors). The dialkylamino substituents were responsible for ICT that deactivated excited states and led to considerable decrease of fluorescence and singlet oxygen quantum yields. Photophysical and photochemical properties were compared to corresponding macrocycles that do not bear any donor centers. The data showed high feasibility of ICT in the tetrapyrazinoporphyrazine macrocycle and significantly lower efficiency of this deactivation process in the tribenzopyrazinoporphyrazine type molecules. Considerable effect of non-donor peripheral substituents on ICT was also described. The results imply that tetrapyrazinoporphyrazines may be more suitable for development of new molecules investigated in applications based on ICT.     

Syntheses of octasubstituted zinc azaphthalocyanines with thiophene or thiophene combined with sulfanyl,amino or imido substituents: Influence of the substituents on photochemical and photophysical properties

Several octasubstituted zinc azaphthalocyanines (ZnAzaPcs) of the tetrapyrazinoporphyrazine type have been synthesized as potential sensitizers for photodynamic therapy (PDT). Octasubstituted complexes, with thiophen-2-yl, thiophen-3-yl or benzo[b]thiophen-3-yl peripheral groups, were synthesized and characterized. Octa(thiophen-2-yl) ZnAzaPc is a better singlet oxygen producer and has a red shifted UV absorption Q-band compared to both thiophen-3-yl and benzo[b]thiophen-3-yl substituted ZnAzaPcs. Thus, the thiophen-2-yl substituent is better suited for our purpose. Unsymmetrically substituted ZnAzaPcs were synthesized by cyclotetramerisations of pyrazine-2,3-dicarbonitriles attached to one thiophen-2-yl group and one alkylsulfanyl, thiomorpholinyl or imide group. Constitutional isomers were detected by NMR spectroscopy for some of these complexes. Compared to unsubstituted ZnAzaPc, red shifted Q-bands were observed for all these complexes, due to the presence of thiophen-2-yl groups. The least promising complexes are ZnAzaPcs with thiomorpholine or imide peripheral substituents, i.e. where the peripheral substituents are attached to the macrocycle through nitrogen atoms. Low singlet oxygen quantum yields (Φ_Δ) and also low fluorescence quantum yields (Φ_F) were observed for these ZnAzaPcs. In the case of combined thiophen-2-yl and alkylsulfanyl substituents, the values of Φ_Δ were the highest and reached values of approximately 0.69.     

Synthesis,characterization and fluorescence behavior of new fluorescent probe phthalocyanines bearing coumarin substituents

In this study, we report a new ligand, 6-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin, and its fluorescent tetrasubstituted phthalocyanines {M[Pc(OBzCou)₄], M = 2H, Zn(II), Co(II); Bz: Benzene}. The effect of the coumarin derivative on the intensity of the fluorescence spectra of the metal-free (H₂Pc) and zinc phthalocyanine (ZnPc) derivatives was investigated. The change of the emission properties of both the coumarin moieties and the phthalocyanine core in the presence of the metal ion and the ring-opening reaction of the coumarin were studied by means of steady-state fluorescence spectroscopy. The radiative decay of the Pcs and the treated coumarin substituents bound to the Pcs was examined. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, Maldi-TOF, IR and UV–Vis spectral data. The photophysical properties of the Pcs are extensively affected by their state of aggregation: in particular, dimerization and aggregation result in a remarkable modification of the absorption and emission bands and may induce significant quenching of the usually strong Pc fluorescence. The electronic spectra exhibit a band of coumarin identity together with characteristic Q and B bands of the phthalocyanine core.     

Synthesis, characterization and comparative studies on the photophysical and photochemical properties of metal-free and zinc(II) phthalocyanines with phenyloxyacetic acid functionalities

The synthesis and characterization of new peripherally and non-peripherally tetra-substituted metal-free and zinc(II) phthalocyanines with 2-, 3- and 4-phenyloxyacetic acid functionalities are described for the first time in this study. The new compounds have been characterized by elemental analysis, FT-IR, UV-Vis, MALDI-TOF and ¹H-NMR spectra. Photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds are studied in dimethylformamide (DMF). The influence of the substituent position on the phthalocyanine framework (non-peripherally or peripherally), central metal ion (metal-free or zinc) and the position of the COOH group (2-, 3- or 4-position on the phenyloxyacetic acid) on the spectroscopic, photophysical and photochemical properties have been investigated. Non-peripherally zinc(II) phthalocyanines (1b and 2b) and peripherally zinc(II) phthalocyanine (4b) gave good singlet oxygen quantum yields (Φ_Δ) (0.37, 0.39 and 0.38, respectively) which indicate the potential of the complexes as photosensitizers in applications of PDT.     

Synthesis, photophysical and photochemical properties of aryloxy tetra-substituted gallium and indium phthalocyanine derivatives

The synthesis, photophysical and photochemical properties of the tetra-substituted aryloxy gallium(III) and indium(III) phthalocyanines are reported for the first time. General trends are described for photodegradation, singlet oxygen, fluorescence, and triplet quantum yields and triplet lifetimes of these compounds. The introduction of phenoxy and tert-butylphenoxy substituents on the ring resulted in lowering of fluorescence quantum yields and lifetimes, and triplet quantum yields, and an increase of k_IC, k_ISC, and k_F. Photoreduction of the complexes was observed during laser flash photolysis. The singlet oxygen quantum yields (Φ_Δ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.41 to 0.91. Thus, these complexes show potential as Type II photosensitizers.     

Red-emitting dyes with photophysical and photochemical properties controlled by pH

New unsymmetrical zinc azaphthalocyanines, bearing one substituted aniline as a peripheral substituent, were prepared by using a statistical condensation approach. Both fluorescence and singlet oxygen quantum yields were extremely low in DMF (Φ(F)<0.01, Φ(Δ)<0.02, respectively), but increased after the addition of sulfuric acid, reaching values comparable to controls without aniline substituents (Φ(F)=0.22-0.29, Φ(Δ)=0.40-0.59, respectively). This behavior was attributed to the deactivation of excited states by intramolecular charge transfer from a donor site (aniline), which was blocked after protonation in acidic media. In the protonated form, all of the compounds efficiently emitted light with λ(em) in the region of 662-675 nm. The investigated compounds were anchored to dioleoylphosphatidylcholine (DOPC) unilamellar vesicles and showed response to buffer pH. They were highly fluorescent at low pH values and almost nonfluorescent in neutral solutions. The pK(a) values were determined in DOPC vesicles and ranged between 2.2 and 4.2.     

Synthesis,characteristics and photochemical studies of novel porphyrazines possessing peripheral 2,5-dimethylpyrrol-1-yl and dimethylamino groups

The synthesis and physicochemical properties of novel porphyrazines possessing an alternate system of two peripheral substituents, 2,5-dimethylpyrrol-1-yl and dimethylamino, are presented. All the macrocycles were subjected to HPLC purity studies. Spectroscopic studies of magnesium(II) porphyrazine encompassed steady state absorption, emission measurements, including fluorescence decays, transient absorption spectra, and thermoluminescence. Additionally, magnesium(II) porphyrazine was found to be a moderate photosensitizer with singlet oxygen generation values of 0.12 and 0.14 in DMF and DMSO, respectively. Comparison of the quantum yields of singlet oxygen generation before and after deoxygenation showed that the photodynamic effect of magnesium(II) porphyrazine is governed by the photosensitization mechanism II. Magnesium(II) and manganese(III) porphyrazines were characterized using X-ray crystallography.     

新型萘四酰亚胺类长波长荧光染料的构建及其光谱调控

本文通过杂环胺类对二溴萘四酰亚胺的亲核反应,分别设计合成了8个未见报道的基于萘四酰亚胺母体的新型单取代或者双取代荧光染料.系统性光谱研究表明,胺类的推电子作用差异可以很好地调控其吸收和荧光波长,使之成为一类性能良好的可见或长波长荧光染料(最大吸收509—580 nm;最大发射565—638 nm;荧光量子效率0.21—0.54;Stokes位移36—77 nm).     

Conformational effects of bay substituents on optical, electrochemical and dynamic properties of perylene bisimides: macrocyclic derivatives as effective probes

A series of diagonally and laterally bridged regioisomeric macrocycles based on 1,6,7,12-tetraaryloxy-substituted perylene bisimides (APBIs) have been synthesized and characterized. The different orientations of the aryloxy residues, that is, horizontal or perpendicular to the perylene core, in the regioisomeric macrocycles have been elucidated by NMR spectroscopy, and the dynamic properties of the laterally bridged regioisomers have been investigated by temperature-dependent NMR measurements. The influence of the different orientations of the aryloxy substituents on the electrochemical properties of APBIs is demonstrated by cyclic voltammetry, which reveals that a perpendicular orientation of the aryloxy residues relative to the perylene core leads to a substantial decrease of the LUMO energy level of the perylene bisimide electrophore. The optical properties of the regioisomeric macrocycles have been determined by UV/Vis and fluorescence spectroscopy. It has been shown that the diagonally bridged macrocycles exhibit optical properties that differ significantly from those of an open-chain reference compound, whereas the optical properties of the laterally bridged isomers resemble those of the reference system. This demonstrates that unrestricted aryloxy substituents prefer the lateral conformation in solution. Solvent-dependent fluorescent properties have been exemplified for one diagonally bridged derivative, suggesting a photoinduced electron transfer process as fluorescence quenching mechanism for APBIs. From these investigations, guidelines toward highly fluorescent APBI dyes in polar media could be derived.     

Synthesis, photophysical and photochemical properties of poly(oxyethylene)-substituted zinc phthalocyanines

The synthesis, photophysical and photochemical properties of the tetra- and octa-poly(oxyethylene)substituted zinc (II) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The effects of the substituents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (3a, 5a and 6a) are also reported. The singlet oxygen quantum yields (Phi(Delta)), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.60 to 0.72. Thus, these complexes show potential as Type II photosensitizers. The fluorescence of the complexes was quenched by benzoquinone (BQ).     

Solvent and central metal effects on the photophysical and photochemical properties of 4-benzyloxybenzoxy substituted phthalocyanines

The synthesis and characterization of new peripherally tetra-4-benzyloxybenzoxy substituted metal-free, zinc and lead phthalocyanines are described for the first time in this study. The influence of various organic solvents and the nature of the central metal ion on the spectroscopic, photophysical and photochemical properties has been investigated. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in different solvents. Photophysical and photochemical properties of phthalocyanine compounds are very useful for photodynamic therapy applications. Especially high singlet oxygen quantum yields are very important for Type II mechanism. The studied phthalocyanine compounds showed good singlet oxygen generation and these compounds show potential as Type II photosensitizers. The fluorescences of the studied compounds are effectively quenched by 1,4-benzoquinone in different solvents.     

Synthesis Efforts of Acyclic Bis(monoalkylamino)maleonitriles and Macrocyclic Bis(dialkylamino)maleonitriles as Fluorescent Probes for Cations and a New Colorimetric Copper(II) Chemodosimeter

In this article, we report on the synthesis of acyclic bis(monoalkylamino)maleonitriles and on the intended synthesis of macrocyclic bis(dialkylamino)maleonitriles to get fluorescent probes for cations. During our efforts to synthesize macrocyclic bis(dialkylamino)maleonitriles, we were only able to isolate macrocyclic bis(dialkylamino)-fumaronitriles. The synthesis of macrocyclic bis(dialkylamino)maleonitriles is challenging, due to the fact that bis-(dialkylamino)fumaronitriles are thermodynamically more stable than the corresponding bis(dialkylamino)-maleonitriles. Further, it turned out that the acyclic bis(monoalkylamino)maleonitriles and macrocyclic bis-(dialkylamino)fumaronitriles are no suitable tools to detect cations by a strong fluorescence enhancement. Further, only the bis(monoalkylamino)maleonitriles, which are bearing a 2-pyridyl unit as an additional complexing unit, are able to selectively recognize copper(II) by a color change from yellow to red.     

Effect of peripheral substitution on the electronic absorption and fluorescence spectra of metal-free and zinc phthalocyanines

The effect of substituents on the position and intensity of the electronic absorption and fluorescence spectra of phthalocyanines (Pcs) was examined for 35 Pc compounds. When electron-releasing groups are bound to four alpha-benzo positions of the Pc skeleton, the B and Q bands shift to longer wavelength. Relative to this shift, the effect of introducing the same electron-releasing groups at the other four alpha positions amounts to about 1.6-2.0. Although the effect is not always clearly seen, introduction of electron-releasing groups in the beta-benzo positions of the Pc skeleton generally shifts the Q band to shorter wavelength. The effect of electron-withdrawing groups is exactly the opposite with respect to the alpha and beta positions. These effects can be reasonably explained by considering the magnitude of the atomic orbital coefficients of the carbon atoms derived from molecular orbital (MO) calculations. In addition, the following intriguing phenomena were observed in the experiments, although not all were explained theoretically: 1) the splitting of the Q band of metal-free Pcs decreases with increasing wavelength of the Q band, 2) the ring currents of Pcs with Q bands at longer wavelength are generally smaller, and 3) the absorption coefficients of the Q band of Pc compounds with 16-electron-releasing substituents are larger than those of the corresponding tetra- and octasubstituted Pcs by several tens of percent. 4) Our PPP calculations suggested that the absorption coefficient of the Q band of Pcs with more strongly electron releasing substituents is larger. 5) The second HOMO of the Pcs with the Q band at longer wavelength has b(1u) symmetry, as opposed to the a(2u) symmetry of normal Pcs. 6) Pcs showing S1 emission maxima at wavelengths longer than about 740 nm generally have quantum yields of less than 0.1.     

Effects of substituents on synthetic analogs of chlorophylls. Part 1: Synthesis, vibrational properties and excited-state decay characteristics

Understanding the effects of substituents on the spectra of chlorins is essential for a wide variety of applications. Recent developments in synthetic methodology have made possible systematic studies of the properties of the chlorin macrocycle as a function of diverse types and patterns of substituents. In this paper, the spectral, vibrational and excited-state decay characteristics are examined for a set of synthetic chlorins. The chlorins bear substituents at the 5,10,15 (meso) positions or the 3,13 (beta) positions (plus 10-mesityl in a series of compounds) and include 24 zinc chlorins, 18 free base (Fb) analogs and one Fb or zinc oxophorbine. The oxophorbine contains the keto-bearing isocyclic ring present in the natural photosynthetic pigments (e.g. chlorophyll a). The substituents cause no significant perturbation to the structure of the chlorin macrocycle, as evidenced by the vibrational properties investigated using resonance Raman spectroscopy. In contrast, the fluorescence properties are significantly altered due to the electronic effects of substituents. For example, the fluorescence wavelength maximum, quantum yield and lifetime for a zinc chlorin bearing 3,13-diacetyl and 10-mesityl groups (662 nm, 0.28, 6.0 ns) differ substantially from those of the parent unsubstituted chlorin (602 nm, 0.062, 1.7 ns). Each of these properties of the lowest singlet excited state can be progressively stepped between these two extremes by incorporating different substituents. These perturbations are associated with significant changes in the rate constants of the decay pathways of the lowest excited singlet state. In this regard, the zinc chlorins with the red-most fluorescence also have the greatest radiative decay rate constant and are expected to have the fastest nonradiative internal conversion to the ground state. Nonetheless, these complexes have the longest singlet excited-state lifetime. The Fb chlorins bearing the same substituents exhibit similar fluorescence properties. Such combinations of factors render the chlorins suitable for a range of applications that require tunable coverage of the solar spectrum, long-lived excited states and red-region fluorescence.     

Singlet and triplet energy transfers in tetra-(meso-truxene)zinc(II)- and tetra-(meso-tritruxene)zinc(II) porphyrin and porphyrin-free base dendrimers

The synthesis, optical properties, and energy transfer features of four dendrimers composed of meso-tetrasubstituted zinc(II) porphyrin (ZnP) or a free base (P) central core, where the substituents are four truxene (Tru) or four tritruxene dendrons (TriTru), TruP, TriTruP, TruZnP, and TriTruZnP, are reported. Selective excitation of the truxene donors results in a photoinduced singlet energy transfer from the truxenes to the porphyrin acceptor. The rates for singlet energy transfer (k(ET)), evaluated from the change in the fluorescence lifetime of the donors (Tru and TriTru) in the presence and absence of the acceptor (P or ZnP) for TruP, TruZnP, TriTruP, and TriTruZnP, are 5.9, 1.2, 0.87, and 0.74 (ns)(-1) at 298 K and 2.6, 2.6, 2.7, and 1.2 (ns)(-1) at 77 K, respectively. A slow triplet-triplet energy transfer from truxene to porphyrin cores in glassy 2MeTHF at 77 K is also reported with rates of 1.3 × 10(3) and 0.10 × 10(2) s(-1) for TruZnP and TriTruZnP, respectively. If the Dexter mechanism for the triplet energy transfers is considered, these slow rates are easily explained by a poor orbital overlap between the truxene and porphyrin π systems. The fluorescence quantum yields (Φ(F)) are 0.20 and 0.16 for TruP and TriTruP and 0.08 and 0.10 for TruZnP and TriTruZnP, respectively at 298 K. At 298 K, a phosphorescence from TruZnP at 795 nm was also observed and is associated with the ZnP chromophore.     

Potential photosensitizers for photodynamic therapy. III. Photophysical properties of a lipophilic chlorin and its zinc and tin chelates.

Photophysical properties of a lipophilic chlorin derivative and its zinc and tin chelates were investigated in chloroform. The quantum yields of the fluorescence phi F, of the S1----T1 intersystem crossing phi T and of singlet oxygen (1 delta g) formation phi delta, as well as the Stern-Volmer constants for the quenching of the S1 states by oxygen and the rate constants of quenching of O2(1 delta g) by the chlorins were measured. In comparison to the metal-free chlorin an increase of phi T and a decrease of phi F have been observed for the metal-containing derivatives, whereas the phi delta values remain constant.     

Synthesis,photophysics, and photochemistry of peripherally Schiff base-zinc complex substituted zinc phthalocyanine

The content of this work is based on the introduction of the salicylhydrazone-zinc complexes into the phthalocyanine core. The reaction of the salicylhydrazone substituted ZnPc (1) with the related zinc(II) salt in basic conditions in DMF yielded bis[bis(salicyhydrazone)phenoxy)zinc(II)] phthalocyaninato zinc(II) (5) in which two salicylhydrazone-Zn complexes are linked through oxygen bridges to the macrocyclic core as three-nuclear complex. The novel compound synthesized in this study was fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, ¹H NMR, ¹³C NMR, elemental analysis and mass spectroscopy. In addition, spectral, photophysical (fluorescence quantum yields), and photochemical (generation of singlet oxygen and photo stability under light irradiation) properties of newly synthesized phthalocyanine (5) and the starting Pcs molecules used to obtain this molecule were investigated in DMSO solutions, comparatively.     

Phosphonic acid functionalized asymmetric phthalocyanines: synthesis, modification of indium tin oxide, and charge transfer

Metalated and free-base A(3)B-type asymmetric phthalocyanines (Pcs) bearing, in the asymmetric quadrant, a flexible alkyl linker of varying chain lengths terminating in a phosphonic acid (PA) group have been synthesized. Two parallel series of asymmetric Pc derivatives bearing aryloxy and arylthio substituents are reported, and their synthesis and characterization through NMR, combustion analysis, and MALDI-MS are described. We also demonstrate the modification of indium tin oxide (ITO) substrates using the PA functionalized asymmetric Pc derivatives and monitoring their electrochemistry. The PA functionalized asymmetric Pcs were anchored to the ITO surface through chemisorption and their electrochemical properties characterized using cyclic voltammetry to investigate the effects of PA structure on the thermodynamics and kinetics of charge transfer. Ionization energies of the modified ITO surfaces were measured using ultraviolet photoemission spectroscopy.     

Chlorin–Bacteriochlorin Energy‐transfer Dyads as Prototypes for Near‐infrared Molecular Imaging Probes: Controlling Charge‐transfer and Fluorescence Properties in Polar Media

The photophysical properties of two energy‐transfer dyads that are potential candidates for near‐infrared (NIR) imaging probes are investigated as a function of solvent polarity. The dyads ( FbC‐FbB and ZnC‐FbB ) contain either a free base (Fb) or zinc (Zn) chlorin (C) as the energy donor and a free base bacteriochlorin (B) as the energy acceptor. The dyads were studied in toluene, chlorobenzene, 1,2‐dichlorobenzene, acetone, acetonitrile and dimethylsulfoxide (DMSO). In both dyads, energy transfer from the chlorin to bacteriochlorin occurs with a rate constant of ～(5–10 ps)^?1 and a yield of >99% in nonpolar and polar media. In toluene, the fluorescence yields (Φ _f = 0.19) and singlet excited‐state lifetimes (τ～5.5 ns) are comparable to those of the benchmark bacteriochlorin. The fluorescence yield and excited‐state lifetime decrease as the solvent polarity increases, with quenching by intramolecular electron (or hole) transfer being greater for FbC‐FbB than for ZnC‐FbB in a given solvent. For example, the Φ _f and τ values for FbC‐FbB in acetone are 0.055 and 1.5 ns and in DMSO are 0.019 and 0.28 ns, whereas those for ZnC‐FbB in acetone are 0.12 and 4.5 ns and in DMSO are 0.072 and 2.4 ns. The difference in fluorescence properties of the two dyads in a given polar solvent is due to the relative energies of the lowest energy charge‐transfer states, as assessed by ground‐state redox potentials and supported by molecular‐orbital energies derived from density functional theory calculations. Controlling the extent of excited‐state quenching in polar media will allow the favorable photophysical properties of the chlorin–bacteriochlorin dyads to be exploited in vivo. These properties include very large Stokes shifts (85 nm for FbC‐FbB , 110 nm for ZnC‐FbB ) between the red‐region absorption of the chlorin and the NIR fluorescence of the bacteriochlorin (λ _f = 760 nm), long bacteriochlorin excited‐state lifetime (～5.5 ns), and narrow (≤20 nm) absorption and fluorescence bands. The latter will facilitate selective excitation/detection and multiprobe applications using both intensity‐ and lifetime‐imaging techniques.     

In situ preparation of highly fluorescent dyes upon photoirradiation

Photoswitchable or photoactivatable fluorescent dyes are potentially applicable to ultrahigh density optical memory media as well as super-resolution fluorescence imaging when the dyes are highly fluorescent and have large absorption coefficients. Here, we report on highly fluorescent photochromic dyes, which are initially nonluminous in solution under irradiation with visible light but activated to emit green or red fluorescence upon irradiation with ultraviolet (UV) light. The dyes 5a-9a are sulfone derivatives of 1,2-bis(2-ethyl-6-phenyl(or thienyl)-1-benzothiophen-3-yl)perfluorocyclopentene. It was found that substitution of phenyl or thiophene rings at 6 and 6' positions of the benzothiophene-1,1-dioxide groups is effective to increase the fluorescence quantum yields of the closed-ring isomers over 0.7 and absorption coefficients over 4 × 10(4) M(-1) cm(-1). The phenyl-substituted derivatives 5a-7a undergo photocyclization reactions to produce yellow closed-ring isomers 5b-7b, which emit brilliant green fluorescence at around 550 nm (Φ(F) = 0.87-0.88) under irradiation with 488 nm light. Any absorption intensity change of the closed-ring isomers was not observed even after 100 h storage in the dark at 80 °C. The closed-ring isomers slowly returned to the initial open-ring isomers upon irradiation with visible (λ > 480 nm) light. The ring-opening quantum yields (Φ(C→O)) were measured to be (1.6-4.0) × 10(-4). When the phenyl substituents are replaced with thiophene rings, such as compounds 8a and 9a, the absorption bands of the closed-ring isomers shift to longer than 500 nm. The closed-ring isomers exhibit brilliant red fluorescences at around 620 nm (Φ(F) = 0.61-0.78) under irradiation with 532 nm light. The ring-opening reactions are very slow (Φ(C→O) < 1 × 10(-5)). The fluorescence lifetimes of these sulfone derivatives were measured to be around 2-3 ns, which is much longer than the value of the closed-ring isomer of 1,2-bis(2-methyl-1-benzothiophen-3-yl)perfluorocyclopentene (τ(F) = 4 and 22 ps). The closed-ring isomer 8b in 1,4-dioxane exhibits excellent fatigue resistant property under irradiation with visible light (λ > 440 nm) superior to the stability of Rhodamine 101 in ethanol.