Characterization of Excited-State Electronic Structure in Diblock π-Conjugated Oligomers with Adjustable Linker Electronic Coupling.

Diblock conjugated oligomers are π-conjugated molecules that contain two segments having distinct frontier orbital energies and HOMO-LUMO gap offsets. These oligomers are of fundamental interest to understand how the distinct π-conjugated segments interact and modify their excited state properties. The current paper reports a study of two series of diblock oligomers that contain oligothiophene (Tn) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) segments that are coupled by either ethynyl (-C≡C-) or trans-(-C≡C-)2Pt(II)(PBu3)2 acetylide linkers. In these structures, the Tn segment is electron rich (donor), and the TBT is electron poor (acceptor). The diblock oligomers are characterized by steady-state and time-resolved spectroscopy, including UV-visible absorption, fluorescence, fluorescence lifetimes, and ultrafast transient absorption spectroscopy. Studies are compared in several solvents of different polarity and with different excitation wavelengths. The results reveal that the (-C≡C-) linked oligomers feature a delocalized excited state that takes on a charge transfer (CT) character in more polar media. In the (-C≡C-)2Pt(II)(PBu3)2-linked oligomers, there is weak coupling between the Tn and TBT segments. Consequently, short wavelength excitation selectively excites the Tn segment, which then undergoes ultrafast energy transfer (~1 ps) to afford a TBT-localized excited state.

Photoinduced Energy and Electron Transfer in a 'Two-Point' Bound Panchromatic, Near-Infrared-Absorbing Bis-styrylBODIPY(Zinc Porphyrin)2 - Fullerene Self-Assembled Supramolecular Conjugate.

In the present study, we report a π-extended conjugated molecular cleft, two zinc(II)porphyrin bearing bisstyrylBODIPY (dyad, 1) has been synthesized. The binding of 1 via a 'two-point' metal-ligand coordination of a bis-pyridyl fulleropyrrolidine (2), forming a stable self-assembled supramolecular complex (1:2), has been established. The self-assembled supramolecular complex has been fully characterized by a suite of physico-chemical methods, including TD-DFT studies. From the established energy diagram, both energy and electron transfer events was envisioned. In dyad 1, selective excitation of zinc(II)porphyrin leads to efficient singlet-singlet excitation transfer to (bisstyrly)BODIPY with an energy transfer rate constant, kEnT of 2.56 x 1012 s-1. In complex 1:2, photoexcitation of zinc(II)porphyrin results in ultrafast photoinduced electron transfer with a charge separation rate constant, kCS of 2.83 x 1011 s-1, and a charge recombination rate constant, kCR of 2.51 x 109 s-1. For excitation at 730 nm corresponding to bisstyrylBODIPY, similar results are obtained, where a biexponential with estimated values of kCS 3.44 x 1011 s-1 and 2.97 x 1010 s-1, and a kCR value of 2.10 x 1010 s-1. The newly built self-assembled supramolecular complex has been shown to successfully mimic the early events of the photosynthetic antenna-reaction center events.

Excitation-Wavelength-Dependent Charge Injection and Hole Localization in Diblock Oligomers Anchored to TiO2.

A series of diblock oligomers containing oligothiophene (Tn, n = 4, 5) and 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadizole (TBT) segments, functionalized with carboxylic acid anchoring groups, were prepared and anchored to mesoporous TiO2 films to study wavelength-dependent interfacial electron transfer mechanisms. Thin films of the surface-anchored diblock oligomers contained two absorption bands centered at 400 and 500 nm, corresponding to the Tn and TBT blocks, respectively. Pulsed-laser excitation of the oligomer-sensitized films yielded local excited-states that promoted electron injection into TiO2. The injection pathway was dependent on the excitation wavelength, as electron injection occurred from the oligomer block that was locally excited. Recombination between the injected electron and the oxidized oligomer was sensitive to the bridging unit that separates the oligomer conjugated segments (-C≡C- vs trans-Pt(PBu3)2-). When the bridge facilitated strong coupling between the two blocks (-C≡C- bridge), the excitation wavelength had no effect on the recombination pathway, as the hole was delocalized over the entire oligomer. However, in the weak coupling case (Pt(PBu3)2- bridge), selective excitation resulted in wavelength-dependent hole localization that persisted to the µs time scale, providing control over the recombination pathway by varying the excitation wavelength. Dye-sensitized solar cells (DSSCs) were fabricated by using the diblock oligomers as sensitizers. The photocurrent action spectra were measured, and the absorbed photon-to-current efficiency (APCE) provided further insight into the electron-transfer mechanisms that are operative under continuous illumination.

Photophysics and charge transfer in oligo(thiophene) based conjugated diblock oligomers.

This paper reports an investigation of the electronic structure and photophysical properties of two "diblock" π-conjugated oligomers (T4-TBT and T8-TBT) that feature electron rich tetra(thiophene) (T4) or octa(thiophene) (T8) segments linked to an electron poor 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) moiety. Electrochemistry and UV-visible absorption spectroscopy reveals that the diblock oligomers display redox and absorption features that can be attributed to the Tn and TBT units. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations support the experimental electrochemistry and optical spectroscopy results, suggesting that the frontier orbitals on the diblock oligomers retain characteristics of the individual π-conjugated segments. However, low energy optical transitions are anticipated to arise from Tn to TBT charge transfer. Fluorescence spectroscopy on the diblock oligomers reveals that the oligomers feature strongly solvent dependent fluorescence. In non-polar solvents (hexane, toluene), the emission is structured with a moderate Stokes shift; however, in more polar solvents the emission becomes broader, and red-shifts significantly. Transient absorption spectroscopy on timescales from femtoseconds (fs) to microseconds (µs) reveals that in non-polar solvents excitation produces a singlet excited state (LE) that decays uniformly to the ground state in parallel with intersystem crossing to a triplet state. By contrast, in more polar solvents, excitation produces a very short-lived excited state (1-3 ps) which evolves rapidly into a second excited state that is attributed to the charge transfer (CT) state. The fast dynamics are associated with crossing from the LE state, which is populated initially by photoexcitation, into the CT state, which then decays to the ground state. The photophysical properties and dynamics of the LE and CT excited states are very similar for T4-TBT and T8-TBT, suggesting that the length of the oligo(thiophene) segment does not have a strong influence on the energy, structure or dynamics of the LE and CT excited states.

Effect of bromine substitution on blue phosphorescent trans-(N-heterocyclic carbene)Pt(II) acetylide complexes.

N-heterocyclic carbene complexes of the type trans-(NHC)2PtII(CC-Ar)2 (where Ar = phenyl or substituted phenyl) are of interest as violet and blue phosphors. These complexes emit efficient phosphorescence in solution and in the solid state, and they have been applied as phosphors in organic light emitting diodes. This study explores the effect of bromine substitution on the trans-(NHC)2PtII(CC-Ar)2 chromophore through photophysical studies of a pair of complexes in which the phenyl groups feature either 3,5-dibromo- or 4-monobromo-substituents (IPt-DB and IPt-MB, respectively). The Br atoms were introduced as heavy atom(s) with the aim to enhance spin-orbit coupling and increase the radiative and non-radiative decay rates of the phosphorescent triplet state. Both IPt-MB and IPt-DB exhibit sky-blue phosphorescence in solution and in PMMA matrix. Interestingly, the emission quantum yield and lifetime of IPt-MB are substantially lower compared to IPt-DB in solution. This effect is attributed to a substantially larger non-radiative decay rate in the mono-bromo complex. Analysis of the photophysical data, combined with DFT and TD-DFT calculations, suggest that the difference in photophysical properties of the two complexes is related to the position of the Br-substituents on the phenyl acetylide rings. In short, in IPt-MB, the Br-substituents are located para-to the Pt-CC-unit, and this gives rise to stronger electron-vibrational coupling in the excited state, enhancing the rate of non-radiative decay.

Assembling Artificial Photosynthetic Models in Water Using ß-Cyclodextrin-Conjugated Phthalocyanines as Building Blocks.

Two water-soluble zinc(II) phthalocyanines substituted with two or four permethylated ß-cyclodextrin (ß-CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky ß-CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2-anthraquinonesulfonate (AQ) in water through host-guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady-state and time-resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light-harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron-deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet-singlet energy transfer from the photo-excited ZnTPPS to the phthalocyanine core with a rate constant (kENT ) in the order of 109  s-1 . The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge-separated state.

One- and Two-Photon Activated Release of Oxaliplatin from a Pt(IV)-Functionalized Poly(phenylene ethynylene).

We report a water-soluble poly(phenylene ethynylene) (PPE-Pt(IV)) that is functionalized with oxidized oxaliplatin Pt(IV) units and its use for photoactivated chemotherapy. The photoactivation strategy is based on photoinduced electron transfer from the PPE backbone to oxaliplatin Pt(IV) as an electron acceptor; this process triggers the release of oxaliplatin, which is a clinically used anticancer drug. Mechanistic studies carried out using steady-state and time-resolved fluorescence spectroscopy coupled with picosecond-nanosecond transient absorption support the hypothesis that electron transfer triggers the drug release. Photoactivation is effective, producing oxaliplatin with a good chemical yield in less than 1 h of photolysis (400 nm, 5 mW cm-2). Photorelease of oxaliplatin from PPE-Pt(IV) can also be effected with two-photon excitation by using 100 fs pulsed light at 725 nm. Cytotoxicity studies using SK-OV-3 human ovarian cancer cells demonstrate that without photoactivation PPE-Pt(IV) is not cytotoxic at concentrations up to 10 µM in polymer repeating unit (PRU) concentration. However, following a short period of 460 nm irradiation, oxaliplatin is released from PPE-Pt(IV), resulting in cytotoxicity at concentrations as low as 2.5 µM PRU.

Formation and Photoinduced Electron Transfer in Porphyrin- and Phthalocyanine-Bearing N-Doped Graphene Hybrids Synthesized by Click Chemistry.

Graphene doped with heteroatoms such as nitrogen, boron, and phosphorous by replacing some of the skeletal carbon atoms is emerging as an important class of two-dimensional materials as it offers the much-needed bandgap for optoelectronic applications and provides better access for chemical functionalization at the heteroatom sites. Covalent grafting of photosensitizers onto such doped graphenes makes them extremely useful for light-induced applications. Herein, we report the covalent functionalization of N-doped graphene (NG) with two well-known electron donor photosensitizers, namely, zinc porphyrin (ZnP) and zinc phthalocyanine (ZnPc), using the simple click chemistry approach. Covalent attachment of ZnP and ZnPc at the N-sites of NG in NG-ZnP and NG-ZnPc hybrids was confirmed by using a range of spectroscopic, thermogravimetric and imaging techniques. Ground- and excited-state interactions in NG-ZnP and NG-ZnPc were monitored by using spectral and electrochemical techniques. Efficient quenching of photosensitizer fluorescence in these hybrids was observed, and the relatively easier oxidations of ZnP and ZnPc supported excited-state charge-separation events. Photoinduced charge separation in NG-ZnP and NG-ZnPc hybrids was confirmed by using the ultrafast pump-probe technique. The measured rate constants were of the order of 1010  s,-1 thus indicating ultrafast electron transfer phenomena.

Bottom-Up Approach to Assess the Molecular Structure of Aqueous Poly(N-Isopropylacrylamide) at Room Temperature via Infrared Spectroscopy.

The structure of poly(N-isopropylacrylamide) (PNIPAM) in solution is still an unresolved topic. Here, the PNIPAM structure in water was investigated using a bottom-up approach, involving the monomer, dimer, and trimer, and a combination of infrared (IR) spectroscopies as well as molecular dynamics simulations. The experiments show that the monomer and oligomers exhibit a broad and asymmetric amide I band with two underlying transitions, while PNIPAM presents the same major transitions and a minor one. Analysis of the 2D IR spectra and theoretical modeling of the amide I band indicates that the two transitions of the monomer do not have the same molecular origin as the oligomers and the polymer. In the monomer, the two bands originate from the ultrafast rotation of its ethyl group, which leads to different solvation structures for the various rotational conformers. In the case of the oligomers, the asymmetry and splitting of the amide I band is caused by the vibrational coupling among adjacent amide side chains. Moreover, it is deduced from the simulations that the oligomers have three distinct backbone conformations for neighboring amides. In particular, two of the backbone conformations have a closed and compact structure, while in the third, the backbone is open and elongated. The bottom-up approach allowed us to infer that such backbone conformations exist in PNIPAM as well. Consequently, the two major amide I transitions of the polymer are also assigned to split amide I transitions resulting from the vibrationally coupled nearest-neighboring amides. In contrast, the additional minor transition observed in PNIPAM is assigned to unsolvated amide units of the polymer. The proposed molecular model successfully describes that PNIPAM amide I band changes with temperature in terms of its molecular structure. This new model strongly suggests that PNIPAM does not have a completely random backbone structure, but has distinct backbone conformers between neighboring amides.

Electron and energy transfer in a porphyrin-oxoporphyrinogen-fullerene triad, ZnP-OxP-C60.

A multichromophoric triad, ZnP-OxP-C60 containing porphyrin (ZnTPP hereafter ZnP), oxoporphyrinogen (OxP) and fullerene (C60) has been synthesized to probe the intramolecular dynamics of its electron and energy transfer in relation to the presence of the closely linked electron deficient OxP-C60 'special pair', constructed as a mimic of the naturally occurring photosynthetic antenna-reaction center. The DFT optimized structure of the triad reveals the relative spatial remoteness of the ZnP entity with proximal OxP/C60 entities. Free-energetics of different energy and electron transfer events were estimated using spectral, computational and electrochemical studies, according to the Rehm-Weller approach. Femtosecond transient absorption spectral studies revealed energy transfer from 1ZnP* to OxP to yield ZnP-1OxP*-C60, and electron transfer to yield ZnP˙+-OxP-C60˙- and/or ZnP-OxP˙+-C60˙- charge seperated states. That is, the ZnP entity in the triad operates as both antenna and electron donor to generate relatively long-lived charge separated states thus mimicking the early photoevents of natural photosynthesis.

Assessing the Location of Ionic and Molecular Solutes in a Molecularly Heterogeneous and Nonionic Deep Eutectic Solvent.

Deep eutectic solvents (DES) are emerging sustainable designer solvents viewed as greener and better alternatives to ionic liquids. Nonionic DESs possess unique properties such as viscosity and hydrophobicity that make them desirable in microextraction applications such as oil-spill remediation. This work builds upon a nonionic DES, NMA-LA DES, previously designed by our group. The NMA-LA DES presents a rich nanoscopic morphology that could be used to allocate solutes of different polarities. In this work, the possibility of solvating different solutes within the nanoscopically heterogeneous molecular structure of the NMA-LA DES is investigated using ionic and molecular solutes. In particular, the localized vibrational transitions in these solutes are used as reporters of the DES molecular structure via vibrational spectroscopy. The FTIR and 2DIR data suggest that the ionic solute is confined in a polar and continuous domain formed by NMA, clearly sensing the direct effect of the change in NMA concentration. In the case of the molecular nonionic and polar solute, the data indicates that the solute resides in the interface between the polar and nonpolar domains. Finally, the results for the nonpolar and nonionic solute (W(CO)6) are unexpected and less conclusive. Contrary to its polarity, the data suggest that the W(CO)6 resides within the NMA polar domain of the DES, probably by inducing a domain restructuring in the solvent. However, the data are not conclusive enough to discard the possibility that the restructuring comprises not only the polar domain but also the interface. Overall, our results demonstrate that the NMA-LA DES has nanoscopic domains with affinity to particular molecular properties, such as polarity. Thus, the presented results have a direct implication to separation science.

Triplet photosensitizer-nanotube conjugates: synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates.

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

Exclusive triplet electron transfer leading to long-lived radical ion-pair formation in an electron rich platinum porphyrin covalently linked to fullerene dyad.

The formation of a high-energy, long-lived radical ion-pair by electron transfer exclusively from the triplet excited state, is demonstrated in a newly synthesized platinum porphyrin-fullerene dyad, in which the porphyrin ring is modified with three electron rich triphenylamine entities. The spin selectivity of the electron transfer leading to the formation of the radical ion-pair is demonstrated using time-resolved optical and EPR spectroscopic techniques.

Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes.

Singlet oxygen sensitization involving a class of hemiquinonoid-substituted resorcinarenes prepared from the corresponding 3,5-di-t-butyl-4-hydroxyphenyl-substituted resorcinarenes is reported. Based on variation in the molecular structures, quantum yields comparable with that of the well-known photosensitizing compound meso-tetraphenylporphyrin were obtained for the octabenzyloxy-substituted double hemiquinonoid resorcinarene reported herein. The following classes of compounds were studied: benzyloxy-substituted resorcinarenes, acetyloxy-substituted resorcinarenes and acetyloxy-substituted pyrogallarenes. Single crystal X-ray crystallographic analyses revealed structural variations in the compounds with conformation (i.e., rctt, rccc, rcct) having some influence on the identity of hemiquinonoid product available. Multiplicity of hemiquinonoid group affects singlet oxygen quantum yield with those doubly substituted being more active than those containing a single hemiquinone. Compounds reported here lacking hemiquinonoid groups are inactive as photosensitizers. The term 'fuchsonarene' (fuchson + arene of resorcinarene) is proposed for use to classify the compounds.

Supramolecular ultrafast energy and electron transfer in a directly linked BODIPY-oxoporphyrinogen dyad upon fluoride ion binding.

A directly linked BODIPY-oxoporphyrinogen dyad has been newly synthesized and occurrence of sequential photoinduced energy and electron transfer upon fluoride anion binding to oxoporphyrinogen has been demonstrated by spectral, electrochemical and femtosecond transient absorption studies.

Sc3N@I h -C80 based donor-acceptor conjugate: role of thiophene spacer in promoting ultrafast excited state charge separation.

Light induced charge separation in a newly synthesized triphenylamine-thiophene-Sc3N@I h -C80 donor-acceptor conjugate and its C60 analog, triphenylamine-thiophene-C60 conjugate is reported, and the significance of the thiophene spacer in promoting electron transfer events is unraveled.

Excited-State Charge Transfer in Covalently Functionalized MoS2 with a Zinc Phthalocyanine Donor-Acceptor Hybrid.

The functionalization of MoS2 is of paramount importance for tailoring its properties towards optoelectronic applications and unlocking its full potential. Zinc phthalocyanine (ZnPc) carrying an 1,2-dithiolane oxide linker was used to functionalize MoS2 at defect sites located at the edges. The structure of ZnPc-MoS2 was fully assessed by complementary spectroscopic, thermal, and microscopy imaging techniques. An energy-level diagram visualizing different photochemical events in ZnPc-MoS2 was established and revealed a bidirectional electron transfer leading to a charge separated state ZnPc.+ -MoS2 .- . Markedly, evidence of the charge transfer in the hybrid material was demonstrated using fluorescence spectroelectrochemistry. Systematic studies performed by femtosecond transient absorption revealed the involvement of excitons generated in MoS2 in promoting the charge transfer, while the transfer was also possible when ZnPc was excited, signifying their potential in light-energy-harvesting devices.

Occurrence of excited state charge separation in a N-doped graphene-perylenediimide hybrid formed via 'click' chemistry.

Hetero-atom doped graphene is a two-dimensional material with a band gap, needed to build optoelectronic devices. However, research progress in this area has been sluggish due to synthetic challenges to build energy harvesting materials, especially donor-acceptor type hybrids. In the present study, using click chemistry, we have successfully synthesized a donor-acceptor hybrid comprised of N-doped graphene and perylenediimide (PDI), a well-known electron-accepting photosensitizer. The TGA and XPS results revealed the attachment of the PDI moiety in the hybrid. Ground and excited state interactions were monitored by a variety of spectral and electrochemical techniques. Finally, the ability of the present donor-acceptor hybrid to undergo photoinduced charge separation from singlet excited PDI was systematically probed using femtosecond transient spectral techniques. Evidence of charge separation was possible to achieve from comparison of transient and spectroelectrochemical results. These results suggest the potential use of covalently functionalized, substitutional N-doped graphene as a functional material for building optoelectronic devices.

N-Doped graphene/C60 covalent hybrid as a new material for energy harvesting applications.

N-Doped graphene (N-G) was chemically functionalized by N-alkylation with the well-known electron acceptor C60. The degree of functionalization and the key structural features of the N-G/C60 hybrid were systematically investigated by a number of techniques including thermogravimetric analysis, X-ray photoelectron and Raman spectroscopies and transmission electron and atomic force microscopies. Absorption and electrochemical studies revealed interactions between the N-G and C60 while the fluorescence of C60 within the hybrid was found to be fully quenched. Evidence for the occurrence of excited state charge transfer from the singlet excited C60 to N-G in the hybrid was obtained from femtosecond transient absorption studies covering the visible-near-IR regions. Electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor, methyl viologen, revealed the accumulation of the one-electron reduced product of methyl viologen upon continuous irradiation of the N-G/C60 nanohybrid, thus revealing the utility of this material in photocatalytic energy harvesting applications.

Interfacing Transition Metal Dichalcogenides with Carbon Nanodots for Managing Photoinduced Energy and Charge-Transfer Processes.

Exfoliated semiconducting MoS2 and WS2 were covalently functionalized with 1,2-dithiolane-modified carbon nanodots (CNDs). The newly synthesized CND-MoS2 and CND-WS2 hybrids were characterized by spectroscopic, thermal, and electron microscopy imaging methods. Based on electronic absorption and fluorescence emission spectroscopy, modulation of the optoelectronic properties of TMDs by interfacing with CNDs was accomplished. Electrochemical studies revealed facile oxidation of MoS2 over WS2 in the examined hybrids, suggesting it to be better electron donor. Excited state events, investigated by femtosecond transient absorption spectroscopic studies, revealed ultrafast energy transfer from photoexcited CNDs to both MoS2 and WS2. Interestingly, upon MoS2 photoexcitation, charge transfer from an exciton dissociation path of MoS2 to CNDs, within CND-MoS2, was observed. However, such a process in CND-WS2 was found to be absent due to energetic reasons. The present study highlights the importance of TMD-derived donor-acceptor hybrids in light energy harvesting and optoelectronic applications. Furthermore, the fundamental information obtained from the current results will benefit design strategies and impact the development of additional TMD-based hybrid materials to efficiently manage and perform in electron-transfer processes.