Donor-acceptor Distance Research Articles

Tetrazole and Oxadiazole Derivatives as Thermally Activated Delayed Fluorescence Emitters.

Organic light-emitting diodes (OLEDs) are promising lighting solutions for sustainability and energy efficiency. Incorporating thermally activated delayed fluorescence (TADF) molecules enables OLEDs to achieve internal quantum efficiency (IQE), in principle, up to 100 %; therefore, new classes of promising TADF emitters and modifications of existing ones are sought after. This study explores the TADF emission properties of six designed TADF emitters, examining their photophysical responses using experimental and theoretical methods. The design strategy involves creating six distinct types of a donor-acceptor (D-A) system, where tert-butylcarbazoles are used as donors, while the acceptor component incorporates three different functional groups: nitrile, tetrazole and oxadiazole, with varying electron-withdrawing character. Additionally, the donor-acceptor distance is adjusted using a phenylene spacer, and its influence on TADF functionality is examined. The clear dependency of an additional spacer, inhibiting TADF, could be revealed. Emitters with a direct donor-acceptor connection are demonstrated to exhibit TADF moderate emissive behavior. The analysis emphasizes the impact of charge transfer, singlet-triplet energy gaps (ΔEST), and other microscopic parameters on photophysical rates, permitting TADF. Among the emitters, TCz-CN shows optimal performance as a blue-green emitter with an 88 % photoluminescence quantum yield (PLQY) and fast rate of reversible intersystem crossing of 2×106 s-1 and 1×107 s-1, obtained from time-resolved photoluminescence (TRPL) experiment in PMMA matrix and quantum mechanical calculations, respectively. This comprehensive exploration identifies molecular bases of superior TADF emitters and provides insights for future designs, advancing the optimization of TADF properties in OLEDs.

First-Principles study on proton transfer in triazole molecules

Triazole can be used as an effective proton carrier because it has one proton donor and two proton acceptors. Density functional theory calculations were performed to explore the proton transfer mechanism of the triazole molecules in gas and solvents. We employed implicit solvent method to analyze the increase of proton donor–acceptor distance (PDAD) in proton transfer mechanism. The solvents reduce the relative energy in tautomers of 1,2,4-triazole molecules, and their protonated form. Proton transfer occurs only at symmetric pairs in the gas, small PDAD, whereas proton transfer in an asymmetric pair is possible in solvents as the PDAD increases.

Maximizing Nanoscale Downshifting Energy Transfer in a Metallosupramolecular Cr(III)-Er(III) Assembly.

Pseudo-octahedral CrIIIN6 chromophores hold a unique appeal for low-energy sensitization of NIR lanthanide luminescence due to their exceptionally long-lived spin-flip excited states. This allure persists despite the obstacles and complexities involved in integrating both elements into a metallosupramolecular assembly. In this work, we have designed a structurally optimized heteroleptic CrIII building block capable of binding rare earths. Following a complex-as-ligand synthetic strategy, two heterometallic supramolecular assemblies, in which three peripherical CrIII sensitizers coordinated through a molecular wire to a central ErIII or YIII, have been prepared. Upon excitation of the CrIII spin-flip states, the downshifted Er(4I13/2 → 4I15/2) emission at 1550 nm was induced through intramolecular energy transfer. Time-resolved experiments at room temperature reveal a CrIII → ErIII energy transfer of 62-73% efficiencies with rate constants of about 8.5 × 105 s-1 despite the long donor-acceptor distance (circa 14 Å). This efficient directional intermetallic energy transfer can be rationalized using the Dexter formalism, which is promoted by a rigid linear electron-rich alkyne bridge that acts as a molecular wire connecting the CrIII and ErIII ions.

(Invited) Distance Dependent Electron Transfer Kinetics in Water Soluble Axially Connected Silicon Phthalocyanine-Fullerene Conjugates

The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine – C60 dyads has been investigated. Herein we will presented the synthesis and photophysical properties of two water soluble C60-SiPc-C60 dyads, 1 and 2, varying in their donor-acceptor distance.In previous investigation for C60-SiPc-C60 dyads where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with k cs equal to 2.7 x 109 s-1 in benzonitrile. However, in the case of C60-SiPc-C60, where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, k cs equal to 9.1 x108 s-1 was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ~ 4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ~3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested that the final lifetime of charge separated state to be in the 3-20 ns range. Energy level diagram established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc .+ -C60 .- charge separated states (1.57 eV) to populate the low-lying 3SiPc* (1.26 eV) prior returning to the ground state.[1]Here we will present our recent results using water soluble SiPc-C60 1-2 systems where the SiPc is substituted with pyridine units.[3]AcknowledgmentsThis work was supported by the Ministerio de Ciencia e Innovación of Spain and FEDER funds (Grants PID2020-117855RB-I00 to ASS) and National Science Foundation (Grant No. 1401188 and 2000988 to FD).References L. Martín-Gomis, S. Seetharaman, D. Herrero, P. A. Karr, F. Fernández-Lázaro, F. D’Souza, and Á. Sastre-Santos, Chem Phys. Chem., 2020, 21, 2254-2262.V. Sobrino, L. Martín-Gomis, S. Seetharaman, P. A. Karr, D’Souza, and Á. Sastre-Santos, under preparation. Figure 1

Proton-Coupled Electron Transfer upon Oxidation of Tyrosine in a De Novo Protein: Analysis of Proton Acceptor Candidates.

Redox-active residues, such as tyrosine and tryptophan, play important roles in a wide range of biological processes. The α3Y de novo protein, which is composed of three α helices and a tyrosine residue Y32, provides a platform for investigating the redox properties of tyrosine in a well-defined protein environment. Herein, the proton-coupled electron transfer (PCET) reaction that occurs upon oxidation of tyrosine in this model protein by a ruthenium photosensitizer is studied by using a vibronically nonadiabatic PCET theory that includes hydrogen tunneling and excited vibronic states. The input quantities to the analytical nonadiabatic rate constant expression, such as the diabatic proton potential energy curves and associated proton vibrational wave functions, reorganization energy, and proton donor-acceptor distribution functions, are obtained from density functional theory calculations on model systems and molecular dynamics simulations of the solvated α3Y protein. Two possible proton acceptors, namely, water or a glutamate residue in the protein scaffold, are explored. The PCET rate constant is greater when glutamate is the proton acceptor, mainly due to the more favorable driving force and shorter equilibrium proton donor-acceptor distance, although contributions from excited vibronic states mitigate these effects. Nevertheless, water could be the dominant proton acceptor if its equilibrium constant associated with hydrogen bond formation is significantly greater than that for glutamate. Although these calculations do not definitively identify the proton acceptor for this PCET reaction, they elucidate the conditions under which each proton acceptor can be favored. These insights have implications for tyrosine-based PCET in a wide variety of biochemical processes.

Using Adiabatic Energy Splitting To Compute Dexter Energy Transfer Couplings.

Dexter energy transfer and transport (DET) are of broad interest in energy science, and DET rates depend on electronic couplings between donor and acceptor species. DET couplings are challenging to compute since they originate from both one- and two-particle interactions, and the strength of this interaction drops approximately exponentially with donor-acceptor distances. Using adiabatic energy splitting to compute DET couplings has advantages because adiabatic states can be calculated directly using conventional quantum chemical methods. We describe a minimum energy splitting method to compute the DET coupling by altering molecular geometries to drive the systems into a T1/T2 energy quasi-degenerate-activated DA complex. We explore the accuracy of various quantum chemical approaches to calculate the Dexter couplings.

Spacer dependence of exciplex dynamics in donor/spacer/acceptor layers

Exciplexes are crucial in organic optoelectronic devices since well-elaborated charge-transfer (CT) complexes exhibit unique exciton generation behavior. Thus, understanding the CT energy structures with exciton dynamics depending on donor–acceptor separation distances is essential for extracting their full potential. In this study, we investigated a long-range exciplex behavior between the electron donor of tris(4-carbazoyl-9-ylphenyl)amine (TCTA) and the electron acceptor of 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T) by finely controlling their distance with 1,4-bis(triphenylsilyl)benzene (UGH-2) as a spacer layer. We report the characteristic exciplex photophysical kinetic behavior with time-dependent dynamics in terms of the donor–acceptor distance associated with the singlet–triplet energy gap and activation energy variation.

Surfactant-Assisted Förster Resonance Energy Transfer from a Quantum Dot Complex for Highly Stable White Light Emission.

Herein we report the fabrication of a surfactant modified quantum dot complex (S-QDC, having λem = 485 nm) nanocomposite (composed of cetyltrimethylammonium bromide surfactants and a zinc-quinolate complex attached ZnS quantum dot), the donor capability of S-QDC in Förster resonance energy transfer (FRET) with an acceptor organic molecule (λem = 573 nm), and finally their utilization in the FRET-based white light emission having features near to mid-day sunlight. The Förster distance, energy transfer efficiency, donor-acceptor distance, number of binding sites, and binding constant are evaluated to be 3.48 nm, 85.74%, 2.58 nm, 0.94, and 1.87 × 104 M-1, respectively, for the current electrostatically driven FRET pair. The solid polymer coated FRET pair composite emits white light having chromaticity color coordinates of (0.33, 0.33) and correlated color temperature of 5350 K and also shows long-term atmospheric white luminescence stability up to 30 days, photostability, and thermal stability with preservation of their pristine morphology.

A molecular dynamics simulation study of glycine/serine octapeptides labeled with 2,3-diazabicyclo[2.2.2]oct-2-ene fluorophore.

The compound 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) is a versatile fluorophore widely used in Förster resonance energy transfer (FRET) spectroscopy studies due to its remarkable sensitivity, enabling precise donor-acceptor distance measurements, even for short peptides. Integrating time-resolved and FRET spectroscopies with molecular dynamics simulations provides a robust approach to unravel the structure and dynamics of biopolymers in a solution. This study investigates the structural behavior of three octapeptide variants: Trp-(Gly-Ser)3-Dbo, Trp-(GlyGly)3-Dbo, and Trp-(SerSer)3-Dbo, where Dbo represents the DBO-containing modified aspartic acid, using molecular dynamics simulations. Glycine- and serine-rich amino acid fragments, common in flexible protein regions, play essential roles in functional properties. Results show excellent agreement between end-to-end distances, orientational factors from simulations, and the available experimental and theoretical data, validating the reliability of the GROMOS force field model. The end-to-end distribution, modeled using three Gaussian distributions, reveals a complex shape, confirmed by cluster analysis highlighting a limited number of significant conformations dominating the peptide landscape. All peptides predominantly adopt a disordered state in the solvent, yet exhibit a compact shape, aligning with the model of disordered polypeptide chains in poor solvents. Conformations show marginal dependence on chain composition, with Ser-only chains exhibiting slightly more elongation. This study enhances our understanding of peptide behavior, providing valuable insights into their structural dynamics in solution.

Natural Pigments-Based Two-Component White Light Emitting Systems.

In this paper, a new class of two component white light emitting systems viz, JaB (java plum + beetroot) {I}, and CaB (carrot + beetroot) {II} were developed through resonance energy transfer (RET) phenomenon by using a fruit (java plum) and two vegetable (carrot and beetroot) extracts. In these white light emitting systems, java plum and carrot are the donors while beetroot is the acceptor. The primary fluorescent pigments present in the natural extracts (i.e., anthocyanin in java plum, β-carotene in carrot, and betanin in beetroot) were responsible for the white light emission. The CIE (Commission Internationale d'Eclairage) coordinates for I and II were {0.32, 0.34} and {0.33, 0.33}, respectively, in solution phase. Interestingly, the white light emission (WLE) was also achieved in agar-agar gel medium. In gel medium, the CIE values were {0.31, 0.34} and {0.33, 0.32} for I and II, respectively. The donor-acceptor distance (r) for I and II were found to be 0.5 and 0.4nm, respectively. Furthermore, the rate of energy transfer was also quantified with the values of 2.78 × 109s-1 for JaB (I) and 1.02 × 108s-1 for CaB (II) systems. The mechanistic investigation of the two white light systems was further supported by DFT studies.

Structural Effects on the Temperature Dependence of Hydride Kinetic Isotope Effects of the NADH/NAD+ Model Reactions in Acetonitrile: Charge-Transfer Complex Tightness Is a Key.

It has recently frequently been found that the kinetic isotope effect (KIE) is independent of temperature (T) in H-tunneling reactions in enzymes but becomes dependent on T in their mutants. Many enzymologists found that the trend is related to different donor-acceptor distances (DADs) at tunneling-ready states (TRSs), which could be sampled by protein dynamics. That is, a more rigid system of densely populated short DADs gives rise to a weaker T dependence of KIEs. Theoreticians have attempted to develop H-tunneling theories to explain the observations, but none have been universally accepted. It is reasonable to assume that the DAD sampling concept, if it exists, applies to the H-transfer reactions in solution, as well. In this work, we designed NADH/NAD+ model reactions to investigate their structural effects on the T dependence of hydride KIEs in acetonitrile. Hammett correlations together with N-CH3/CD3 secondary KIEs were used to provide the electronic structure of the TRSs and thus the rigidity of their charge-transfer complexation vibrations. In all three pairs of reactions, a weaker T dependence of KIEs always corresponds to a steeper Hammett slope on the substituted hydride acceptors. It was found that a tighter/rigid charge-transfer complexation system corresponds with a weaker T dependence of KIEs, consistent with the observations in enzymes.

Unraveling the mechanism of tip-enhanced molecular energy transfer

Electronic Energy Transfer (EET) between chromophores is fundamental in many natural light-harvesting complexes, serving as a critical step for solar energy funneling in photosynthetic plants and bacteria. The complicated role of the environment in mediating this process in natural architectures has been addressed by recent scanning tunneling microscope experiments involving EET between two molecules supported on a solid substrate. These measurements demonstrated that EET in such conditions has peculiar features, such as a steep dependence on the donor-acceptor distance, reminiscent of a short-range mechanism more than of a Förster-like process. By using state of the art hybrid ab initio/electromagnetic modeling, here we provide a comprehensive theoretical analysis of tip-enhanced EET. In particular, we show that this process can be understood as a complex interplay of electromagnetic-based molecular plasmonic processes, whose result may effectively mimic short range effects. Therefore, the established identification of an exponential decay with Dexter-like effects does not hold for tip-enhanced EET, and accurate electromagnetic modeling is needed to identify the EET mechanism.

Nanometal Surface Energy Transfer (NSET) from Biologically Active Heterocyclic Ligands to Silver Nanoparticles Induces Enhanced Antimicrobial Activity against Gram-positive Bacteria

Herein we report the formation of a nanometal surface energy transfer (NSET) pair between a donor biologically active heterocyclic luminescent ligand such as 3-(1,3-Dioxoisoindolin-2-yl)-N, N-dimethylpropan-1-ammonium perchlorate (S4PNL; λem-408nm) and an acceptor silver nanoparticle (Ag NP; λabs-406nm). When the S4PNL ligand interacts with Ag NPs, the quenching in their luminescence intensity at 408nm is noticed, with a Stern-Volmer constant of 0.8×104 M-1. The present donor-acceptor pair displays a binding constant of 2.8×104 M-1 and binding sites of 1.12. The current work shows the energy transfer from a molecular dipole (S4PNL) to a nanometal surface (Ag NP) and thus follows the nanometal surface energy transfer (NSET) ruler with an energy transfer efficiency of 80.0%, 50% energy transfer efficiency distance (d0) of 4.9nm, donor-acceptor distance of 3.4nm. The alteration in the zeta potential value of S4PNL upon interaction with AgNP clearly demonstrates the strong electrostatic interaction between donor and acceptor. Importantly, the current NSET pair shows enhanced antimicrobial activity against gram-positive bacteria such as Bacillus cereus (B. cereus) in comparison to their parent components i.e. S4PNL ligand and Ag NP. The NSET pair shows maximum inhibition against B. cereus (9202.21±463.26 CFU/ml.) at 10% while minimum inhibition is observed at 0.01% of it (39,887.19±242.67 CFU/ml.).

Polymerization-Mediated Through-Space Charge Transfer: An Emerging Strategy for Light-Emitting Materials.

Through-space charge transfer (TSCT) has attracted increasing attention owing to its great potential in designing efficient light-emitting molecules and polymers. Complementary to through-bond charge transfer and Förster resonance energy transfer, TSCT offers an alternative approach for the manipulation of molecular fluorescence. Recently, the synergy between TSCT and polymer systems through polymerization-mediated charge transfer has fostered the advancements of innovative light-emitting functional materials featuring thermally activated delayed fluorescence and/or aggregation-induced emission. This perspective highlights the significant progress in tailoring emission properties through structural engineering of donor and acceptor groups within polymeric systems, leveraging the TSCT mechanism. This strategy has transcended the limitations of traditional charge transfer systems with its tolerance to extended donor-acceptor distance, paving the way for novel applications beyond organic light-emitting diodes. The discussion concludes with a forward-looking analysis of potential future research trajectories in the field of polymerization-mediated charge transfer for developing next-generation light-emitting materials.

Tunable photo/thermochromic properties of Cd(II)-viologen coordination polymers modulated by coordination modes for flexible imaging films and anti-counterfeiting.

Two photochromic Cd(II)-CPs were obtained based on the viologen ligand using different synthetic routes, named {[Cd4(p-BDC)4(CPB)2(H2O)2]·2H2O·EtOH}n (1) and {[Cd(p-BDC)(CPB)(H2O)]·(L)·DMF}n (2) (p-H2BDC = 1,4-benzene-dicarboxylate, HCPB·Cl = 1-(4-carboxyphenyl)-4,4'-bipyridinium·Cl, L = 2,4-dinitrochlorobenzene, and DMF = N,N-dimethylformamide), respectively. Due to different coordination modes, the two Cd(II)-CPs show different structures. Compound 1 exhibits a three-dimensional (3D) framework with bimetallic nodes, while compound 2 displays a 2-fold interpenetrated (4,4) net topology. Notably, the two Cd(II)-CPs exhibit substantial disparities in photo/thermochromism, which can be attributed to variations in donor-acceptor (D-A) distances arising from structural differences. Compound 1 showed visually sensitive photo- and thermochromic behavior due to multi-pathway electron transfer and short D-A distances, which is relatively rare in electron-transfer type photochromic systems. In contrast, 2 only demonstrates insensitive photochromic behavior, with a slight deepening of the color observed after 2 hours of UV light, which is due to the mono-pathway electron transfer and long D-A distance. Moreover, we first combined Cd(II)-viologen CPs with polydimethylsiloxane (PDMS) to prepare a 1@PDMS flexible UV imaging film. 1@PDMS exhibits excellent bendability and stretchability and maintains good photochromic properties after 100 bending cycles. To demonstrate the rapid color response and distinct color contrast of 1, its application in anti-counterfeiting is also demonstrated.

Micellular fluorescence resonance energy transfer based fluorescent ratiometric response to hydrocarbon analytes.

Fluorescence resonance energy transfer (FRET) has been utilised to develop numerous selective and sensitive fluorescent ratiometric sensors. Typically, FRET-based fluorescent ratiometric sensors rely on chemical interactions between the sensor and analyte to illicit a response, thus unreactive hydrocarbons are a neglected analyte and a source for new sensors. By containing an unbound donor-acceptor system within micelles, energy transfer is enabled by spatial confinement. This offers the potential of a ratiometric response as a hydrocarbon analyte is added. Introducing a hydrocarbon analyte to this system causes micelles to swell, increasing the donor-acceptor distance and thus reducing the amount of observed energy transfer. We present InP/ZnS quantum dot donors interacting with a Nile Red acceptor, confined by cetyltrimethylammonium bromide (CTAB)-based micelles. We alleviated spatial confinement of the pair within micelles using common laboratory solvents to represent hydrocarbons, (toluene, hexane and octadecene). We constructed calibration curves for each solvent and found effective sensing ranges of 0.009-0.21, 0.008-0.27 and 0.003-0.06 M for toluene, hexane and octadecene, respectively. This study contributes towards the development of new hydrocarbon sensors utilising this new mechanism.

Investigating Intramolecular H Atom Transfer Dynamics in β-Diketones with Ultrafast Infrared Spectroscopies and Theoretical Modeling.

The vibrational signatures and ultrafast dynamics of the intramolecular H-bond in a series of β-diketones are investigated with 2D IR spectroscopy and computational modeling. The chosen β-diketones exhibit a range of H atom donor-acceptor distances and asymmetry along the H atom transfer coordinate that tunes the intramolecular H-bond strength. The species with the strongest H-bonds are calculated to have very soft H atom potentials, resulting in highly red-shifted OH stretch fundamental frequencies and dislocation of the H atom upon vibrational excitation. These soft potentials lead to significant coupling to the other normal mode coordinates and give rise to the very broad vibrational signatures observed experimentally. The 2D IR spectra in both the OH and OD stretch regions of the light and deuterated isotopologues reveal broadened and long-lived ground-state bleach signatures of the vibrationally hot molecules. Polarization-sensitive transient absorption measurements in the OH and OD stretch regions reveal notable isotopic differences in orientational dynamics. Orientational relaxation was measured to occur on ∼600 fs and ∼2 ps time scales for the light and deuterated isotopologues, respectively. The orientational dynamics are interpreted in terms of activated H/D atom transfer events driven by collective intramolecular structural rearrangements.

NIR FRET Luminescence in Rhenium Complex and Dye Co‐Loaded Polymer Nanoparticles

AbstractPhotoactive transition‐metal complexes are luminophores combining high photostability and long luminescence lifetimes. However, reduced optical performance in aqueous solutions has limited their use in biological systems. Herein, the physicochemical and photophysical properties and bioimaging compatibility of Re diimine complexes and near‐infrared (NIR) emitting Cy5 dyes coencapsulated in polymer nanoparticles (NPs) are investigated. By varying the polymers, NPs with sizes from 20 to 70 nm and encapsulating ≤ 40 wt.% of Re complexes, i.e., ≈11 000 Re complexes per NP, are obtained. The photoluminescence (PL) quantum yields of the Re complexes increase eightfold to ≈50% upon encapsulation (vs 6–7% in acetonitrile), resulting in PL brightness up to 108 m−1 cm−1 and PL lifetimes of 3–4 µs. Coencapsulation of Cy5 yields very bright NIR emission upon Re complex excitation. Very close Re‐to‐Cy5 donor–acceptor distances down to ≤2 nm and FRET efficiencies over 90% are confirmed by PL lifetime measurements. The Re‐Cy5 NPs enter mammalian cells for high‐contrast PL imaging in both visible and NIR. This detailed characterization provides a better understanding of the photophysical properties of the transition‐metal‐dye FRET NPs and presents a vital step toward the efficient design of a new class of bright luminescent NP probes.

Engineered NIR-II fluorophores with ultralong-distance molecular packing for high-contrast deep lesion identification

The limited signal of long-wavelength near-infrared-II (NIR-II, 900–1880 nm) fluorophores and the strong background caused by the diffused photons make high-contrast fluorescence imaging in vivo with deep tissue disturbed still challenging. Here, we develop NIR-II fluorescent small molecules with aggregation-induced emission properties, high brightness, and maximal emission beyond 1200 nm by enhancing electron-donating ability and reducing the donor-acceptor (D-A) distance, to complement the scarce bright long-wavelength emissive organic dyes. The convincing single-crystal evidence of D-A-D molecular structure reveals the strong inhibition of the π-π stacking with ultralong molecular packing distance exceeding 8 Å. The delicately-designed nanofluorophores with bright fluorescent signals extending to 1900 nm match the background-suppressed imaging window, enabling the signal-to-background ratio of the tissue image to reach over 100 with the tissue thickness of ~4–6 mm. In addition, the intraluminal lesions with strong negatively stained can be identified with almost zero background. This method can provide new avenues for future long-wavelength NIR-II molecular design and biomedical imaging of deep and highly scattering tissues.

A Curated Graphene Quantum Dot-Porphyrin-Based Photosensitizer for Effective Singlet Oxygen Generation through Energy Transfer.

Porphyrin-based photosensitizers are proven generators of reactive oxygen species (ROS), such as singlet oxygen, and used as anti-cancer therapeutic agents. However, most of these compounds suffer from potential drawbacks due to limited photostability, hydrophobicity, aggregation propensity, and low cellular uptake. Ultrasmall fluorescent graphene quantum dots (GQDs) have emerged as the next-generation carriers for drugs and have gained reputation in the pharmaceutical domain. Considering the various limiting factors in porphyrin-based ROS generation and cellular internalization, here, we have developed a method to generate tetrakis(m-nitrophenyl) porphyrin (TNPP)-GQD exciplexes. This allows resonance energy transfer (RET) from GQDs to TNPP. The calculated overlap integrals for GQD-TNPP and AGQD-TNPP (1.001 × 1018 and 1.257 × 1017 M-1 cm-1 nm4, respectively) assured 95 and 71% energy transfer. The optimum donor-acceptor distances in these couples are 59.82 and 62.65 Å, respectively, which yielded the rate constant of RET as 4.09 and 0.56 ns-1, respectively. The efficient RET helped in subsequent generation of singlet oxygen. The singlet oxygen quantum yields (SOQY) of around 0.435 and 0.464 for GQD-TNPP and AGQD-TNPP, respectively, are comparable to those of different porphyrin derivatives where the SOQY ranges from 0.55 to 0.70 when used with Triton X-100. The data show that non-conjugated amine- and amide-functionalized GQDs (AGQDs) are better candidates in this case because of the special properties of the amine groups. The systems could be excited at 450 nm for FRET, which favors biological usage.