Synthesis and conformation of a novel fluorescein–Zn-porphyrin dyad and intramolecular energy transfer

Rezazgui, Olivier; Trouillas, Patrick; Qiu, Shihong; Siegler, Benjamin; Gierschner, Johannes; Leroy‐Lhez, Stéphanie

doi:10.1039/c5nj02901e

Cited by 16 publications

(22 citation statements)

References 67 publications

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“…In a previous publication, we described the synthesis and characterization of a new zinc‐porphyrin‐fluorescein dyad Trz , the porphyrin and fluorescein being covalently linked by a 1,2,3‐triazole bridge . This novel molecule was shown to adopt a folded conformation, confirmed through NOESY and conformational analysis stabilized by CH‐π interaction, as well as a solvent‐dependent and photoinduced intramolecular energy transfer from fluorescein to porphyrin pattern, with an efficiency of about 35%.…”

Section: Introductionsupporting

confidence: 88%

“…These interactions are known to possibly affect photophysical properties including absorption and emission spectra or energy transfer ( vide infra ). In line with our previous study on Trz , and in order to investigate the influence of folding on photophysical properties (in particular on energy transfer), we studied two other linkers bearing different characteristics, namely: 1) a 1,3‐dibromopropane linker (in compound 1 ), allowing flexibility (but less than in Trz dyad) and 2) a 1,4‐dichloro‐2‐butyne linker (in compound 2 ), providing a high degree of rigidity, thus precluding folding.…”

Section: Resultsmentioning

confidence: 99%

“…of 1,3‐dibromopropane at room temperature provided the best results with an 89% yield; an increase of either the quantity of 1,3‐dibromopropane or the temperature led to a decrease in yields. For the sake of comparison in spectroscopic studies, the individual porphyrin 3 , taken as a reference, and its free‐base counterpart 10 described in our previous work were synthesized (Scheme ), by a Williamson's reaction assisted by micro‐waves with 1‐bromopropane on 8 then follow‐up by a metalation sequence (78% yield for the two steps) . Using the same conditions than for 9 or 10 , with 1,4‐dichloro‐2‐butyne, did not form 11 .…”

Section: Resultsmentioning

confidence: 99%

“…In the case of Trz , a fluorescence emission quenching was observed for fluorescein. This was attributed to an intramolecular energy transfer from the first singlet state, centred on fluorescein, to porphyrin, which was favoured in the folded conformation of Trz . Thus, because of its linear structure, a decrease in intramolecular energy transfer was expected for compound 2 .…”

Section: Resultsmentioning

confidence: 99%

“…As in the case of Trz , intramolecular energy transfer in compound 2 cannot be ruled out. Indeed, as outlined in Figure , for an equimolar mixture of 3 and 4 , no fluorescein emission quenching was observed.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Studies of New Fluorescein‐Porphyrin Dyads: A Theoretical and Experimental Approach

et al. 2018

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Synthesis of two new zinc porphyrin fluorescein dyads are reported here. The two chromophoric units are covalently linked by alkane or alkyne bond, which provides various degrees of flexibility. Conformational analysis as photophysical properties were performed both experimentally (NOESY experiments, lifetimes, ROS production…) and theoretically (DFT and TD‐DFT calculations). Comparison with triazole linker described in a precedent study highlighted that linkage nature determine conformational structure (folding/linearity) but do not significantly modify energy transfer between the two moieties involved in dyads.

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Section: Introductionsupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Studies of New Fluorescein‐Porphyrin Dyads: A Theoretical and Experimental Approach

et al. 2018

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Boosting the Stimulated Emission Properties of Host:Guest Polymer Blends by Inserting Chain Twists in the Host Polymer

Sun

Bai

Roldao

et al. 2022

Adv Funct Materials

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Conjugated polymer blends coupled by Förster resonance energy transfer (FRET) have been widely exploited to achieve optically pumped lasers operating at very low pumping thresholds. Among the plaid of conjugated polymers and molecules exploited for optical gain, fluorene‐based polymers are considered front‐runners, based on their high photoluminescence quantum yields, large optical gain coefficients, and their processability assets in films of high optical quality. Two archetypes of polymers with these properties are poly(9,9‐dioctyl‐fluorene) and its green‐emitting relative poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) that work as excellent FRET‐coupled blends but unexpectedly do not exhibit stimulated emission. In this study, light is shed upon the optical gain limiting factors of these blends. Upon investigating a series of poly(diarylfluorene‐co‐N‐phenyl) polymers bearing a different number of phenyl units inserted between the fluorenes (NPhs, N = 1, 2, 3), important improvements are revealed in the photoluminescence quantum yields and stimulated emission properties, as well as harnessing of exciton‐exciton annihilation. These effects are ascribed to disruption of exciton transport in NPhs motivated by changes in chain conformation and molecular packing upon phenyl‐insertion.

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The Second Excited Triplet‐State Facilitates TADF and Triplet–Triplet Annihilation Photon Upconversion via a Thermally Activated Reverse Internal Conversion

Zhao

Chen

et al. 2022

Advanced Optical Materials

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therapy, [2] energy conversion, [3] display and lighting, [4] and time-resolved imaging [5] due to the efficient triplet harvesting and the low biological toxicity, etc. The core of TADF molecules lies in their triplet excitons via a fast reverse intersystem crossing (RISC, k RISC = 10 6 -10 10 s −1 ) process leading to efficient repopulation from the radiative-forbidden triplet states (T 1 ) to radiative-allowed singlet states (S 1 ) with the aid of thermal energy (Scheme 1a). [6] However, the RISC process of triplet excitons of TADF compounds upconverted from the high-lying triplet state (e.g., T 2 ) to S 1 state is yet to be broadly under-recognized. The primary case for this scruple is dependent on the consideration of T 2 − T 1 energy gap: a small T 2 − T 1 energy gap leading to energy dissipation of T 2 excitons via the rapid internal conversion (IC, k IC = 10 12 -10 14 s −1 ) tremendously hinders the effective RISC of T 2 − S 1 ; [7] a rather large T 2 − T 1 gap is expected to impede the IC and then participate the T 2 − S 1 RISC forming the "hot exciton" channel (Scheme 1b) instead of traditional TADF channel. [8] Recent years have seen a surge in organic emitters that exhibit thermally activated delayed fluorescence (TADF) behavior owing to their high exciton utilization efficiency, low biological toxicity, etc. However, the existing TADF channel is insufficiently well developed as to design high-performance materials especially in the high-lying triplet state mediated reverse intersystem crossing process. A thermally activated reverse internal conversion (TARIC) pathway is reported here, which can achieve effective population transfer from T 1 to T 2 states via conical intersection point with the barrier of 3.81 kcal mol −1 . On this basis, the mediated T 2 state facilitates the TADF and triplet-triplet annihilation photon upconversion (TTA-UC) channel. Furthermore, benefited from the TARIC pathway, the designed 2′,7′-dichlorofluorescein (DCF) derivative DCF−MPYM−Me photosensitizer presents an excellent upconversion efficiency of 13.6%. The high upconversion efficiency is the best performance in purely organic TADF photosensitizers without heavy atoms in TTA−UC systems.

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Synthesis and conformation of a novel fluorescein–Zn-porphyrin dyad and intramolecular energy transfer

Abstract: Modulations of the optical properties of a new porphyrin–fluorescein dyad were elucidated using experimental and theoretical techniques, with conformational rearrangements being studied.

Cited by 16 publications

References 67 publications

Synthesis and Studies of New Fluorescein‐Porphyrin Dyads: A Theoretical and Experimental Approach

Synthesis and Studies of New Fluorescein‐Porphyrin Dyads: A Theoretical and Experimental Approach

Boosting the Stimulated Emission Properties of Host:Guest Polymer Blends by Inserting Chain Twists in the Host Polymer

The Second Excited Triplet‐State Facilitates TADF and Triplet–Triplet Annihilation Photon Upconversion via a Thermally Activated Reverse Internal Conversion

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