Structural Influence on Exciton Migration and Singlet Oxygen Photosensitization in Porphyrinic Metal–Organic Coordination Networks

Asselin, Paul; Schlachter, Adrien; Fortin, Daniel; Karsenti, Paul‐Ludovic; Harvey, Pierre D.

doi:10.1021/acs.chemmater.2c01105

Cited by 6 publications

(6 citation statements)

References 101 publications

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Section: Resultsmentioning

confidence: 99%

“…As reported by Asselin et al, structurally enhanced energy migration can induce enhanced singlet oxygen photosensitization due to exciton migration from the mass toward the interface. 58 Indeed, as reported in Figure 14, singlet oxygen generation is rendered obvious using TFT-MOF as a photosensitizer. Such solid−gas interface signals for O 59 So after collision with the surface of the photosensitizer, a maximum distance of 26.4 cm may be traveled by 1 O 2 (g) if in a straight line.…”

Section: Estimating the Rate Of Energymentioning

confidence: 99%

See 1 more Smart Citation

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

Boivin,

Schlachter,

Fortin

et al. 2023

Inorg. Chem.

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A new metal−organic framework (MOF; [Zn 4 O-(hett) 4/3 (fluo) 1/2 (bdc) 1/2 ] n ; TFT-MOF) constructed on chromophoric ligands 5,5′,10,10′,15,15′-hexaethyltruxene-2,7,12-triacetate (hett), 9-fluorenone-2,7-dicarboxylate (fluo), terephthalate (bdc), and the Zn 4 O node has been prepared and identified by powder Xray diffraction. This luminescent MOF exhibits large mesoporous pores of 2.7 nm based on computer modeling using density functional theory (DFT) calculations. The steady-state and timeresolved fluorescence spectra and photophysical parameters of TFT-MOF have been investigated and compared with those of the free ligands and their basic chromophores. All in all, TFT-MOF exhibits particularly efficient singlet−singlet energy-transfer processes described as 1 (hett)* → (fluo) and 1 (bdc)* → (fluo), leading to fluorescence arising for the fluo lumophore operating only through Forster resonance energy transfer (FRET) with an efficiency of transfer of up to >95%. This experimental conclusion was corroborated by DFT and time-dependent DFT (TDDFT). For the 1 (hett)* → (fluo) process, the approximated overall rate constant of energy transfer was evaluated to be at most 2.04 × 10 10 s −1 (using a Stern−Volmer approach of solution data and the relationship between distance and concentration). This process was analyzed using the Forster theory, where two intrapore energy transfer paths of center-to-center distances of 13 and 25 Å have been identified. TFT-MOF photosensitizes the formation of singlet oxygen ( 1 O 2 ( 1 Σ g )) as detected by its phosphorescence signal at 1275 nm.

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Section: Resultsmentioning

confidence: 99%

Section: Estimating the Rate Of Energymentioning

confidence: 99%

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

Boivin,

Schlachter,

Fortin

et al. 2023

Inorg. Chem.

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“…More recently, MOF glasses, a disordered form of MOFs, are finding niche applications. This virtual collection catalogues recent MOF advances featured in Chemistry of Materials from 2022 to 2023, − with an accompanying editorial by Laura Gagliardi and Omar Yaghi that outlines three critical future directions for MOFs …”

Section: Opening Remarksmentioning

confidence: 99%

“…Harvey and co-workers assessed the ability of porphyrin-based MOFs to promote efficient exciton energy migration through singlet–singlet annihilation processes and to photosensitize singlet oxygen ( 1 O 2 ( g )). Interporphyrin couplings favor exciton migration determined by the Donor–Acceptor distance and orientation . In another insightful work on photoactive MOFs, D’Alessandro and co-workers quantified the temperature dependence of the kinetics of a double [2 + 2] photocyclization in photoactive [Cd 2 (stil) 2 (Py2TTF) 2 ] (stil 2– = 4,4′-stilbenedicarboxylic acid, Py2TTF = 2,6-bis(4′-pyridyl)-tetrathiafulvalene) .…”

Section: Conductive and Photoactive Mofsmentioning

confidence: 99%

The Chemistry of Metal Organic Framework Materials

Skrabalak

Vaidhyanathan

2023

Chem. Mater.

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The journal started its 35th year by celebrating 35 recent manuscripts in a virtual issue that highlighted diverse materialsbased research: battery materials, MXenes and layered dichalcogenides, covalent organic frameworks and porous materials, hydrogels, catalysts, photovoltaics and thermoelectrics, luminescent and optical materials, and materials discovery. The subsequent virtual issue on π-Conjugated Materials accentuated how chemical structure and conjugation can shape materials for various applications. Continuing with the theme of designable crystalline materials, we now look at Metal Organic Frameworks (MOFs), whose structure− property investigations have consistently embellished the pages of Chemistry of Materials and advanced their applications. In the last three decades, MOFs have been established as excellent candidates for interlacing complementary functions to realize high surface area materials for molecular separations and gas storage, stimuli-responsive and dynamic crystalline frameworks, and conductive crystalline porous structures. More recently, MOF glasses, a disordered form of MOFs, are finding niche applications. This virtual collection catalogues recent MOF advances featured in Chemistry of Materials from 2022 to 2023, 1−37 with an accompanying editorial by Laura Gagliardi and Omar Yaghi that outlines three critical future directions for MOFs. 38

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“…The efficiency of heterogeneous photocatalysis depends, among several parameters, on the efficiency (i.e., rate and distance) of exciton migration through the framework, − which depends on the framework structure. , We now report the power dependence of the fluorescence intensity and lifetimes of 3D-[Zn 2 (BTTB)(DMF) 2 •(H 2 O) 3 ] n hereafter designated MOF-D (for which no photophysical properties have been reported so far) and MOF-5 as a function of solvent molecules inside the pores (guests). It is found that in both cases, these parameters are strongly dependent on the nature of the guest molecule.…”

Section: Introductionmentioning

confidence: 99%

Strong Host–Guest Dependence on the Emissive Properties of MOF-5 and [Zn₂(BTTB)(DMF)₂•(H₂O)₃]_n

Schlachter,

Asselin,

Fortin

et al. 2023

Inorg. Chem.

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3D-[Zn4O(1,4-BDC)3•x(solvent)] n (MOF-5; BDC = 1,4-benzodicarboxylate) and 3D-[Zn2(BTTB)(DMF)2•(H2O)3] n (MOF-D; BTTB = 4,4′,4″,4‴-benzene-1,2,4,5-tetrayltetrabenzoate) have been investigated by means of steady-state UV–visible and fluorescence and time-resolved emission spectroscopy, as a function of solvent and power of the excitation irradiation. The low-temperature X-ray structures (173 K) were permitted to locate solvent molecules (here H2O) in the lattice. They were found distributed in the middle in the voids with no evidence of specific interactions (H-bond, coulombic, and dipole–dipole) with the framework. The fluorescence decays of the ligands (ππ* excited state), τF, for the host–guest composites MOF-5@solvent and MOF-D@solvent (solvent = air, MeCN, EtCN, MeOH, EtOH, and DMF) were found bi-exponential (short τF1 (ps), and long τF2 (ns)) with one important feature: upon cooling from 298 to 77 K, MOF-5’s τF1 decreases and τF2 increases, while the opposite trend is generally observed in MOF-D. The low values for τF1 (ps) in MOF-5 are associated with the augmented probability of solvent-ligand collisions leading to nonradiative deactivation, which upon cooling to 77 K increases further as the scaffolding contracts. The augmentation in τF2 is readily associated with the increased rigidity of the ligands that are not submitted to this effect (at the surface of the MOF and as pendent groups). For the low emitter MOF-D, the reversed situation is noted but not as clearly due to the uncertainties in the data. Upon increasing the excitation flux, the fluorescence intensity increases linearly with the laser power indicating the absence of singlet–singlet annihilation, inferring the absence of efficient exciton migration. This observation is explained by the small absorptivity coefficients, which leads to a small J spectral overlap between absorption and fluorescence according to the Forster and Dexter theories, and consequently, a small rate for energy migration. This conclusion drastically changes the perception of the photocatalytic mechanism of MOF-5 and other MOFs exhibiting similar absorption features (i.e., no antenna effect).

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Structural Influence on Exciton Migration and Singlet Oxygen Photosensitization in Porphyrinic Metal–Organic Coordination Networks

Cited by 6 publications

References 101 publications

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

The Chemistry of Metal Organic Framework Materials

Strong Host–Guest Dependence on the Emissive Properties of MOF-5 and [Zn₂(BTTB)(DMF)₂•(H₂O)₃]_n

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Structural Influence on Exciton Migration and Singlet Oxygen Photosensitization in Porphyrinic Metal–Organic Coordination Networks

Cited by 6 publications

References 101 publications

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF

The Chemistry of Metal Organic Framework Materials

Strong Host–Guest Dependence on the Emissive Properties of MOF-5 and [Zn2(BTTB)(DMF)2•(H2O)3]n

Contact Info

Product

Resources

About

Strong Host–Guest Dependence on the Emissive Properties of MOF-5 and [Zn₂(BTTB)(DMF)₂•(H₂O)₃]_n