Singlet Exciton Research Articles

Printable Block Molecular Assemblies with Controlled Exciton Dynamics.

Creating hierarchical molecular block heterostructures, with the control over size, shape, optical, and electronic properties of each nanostructured building block can help develop functional applications, such as information storage, nanowire spectrometry, and photonic computing. However, achieving precise control over the position of molecular assemblies, and the dynamics of excitons in each block, remains a challenge. In the present work, the first fabrication of molecular heterostructures with the control of exciton dynamics in each block, is demonstrated. Additionally, these heterostructures are printable and can be precisely positioned using Direct Ink Writing-based (DIW) 3D printing technique, resulting in programable patterns. Singlet excitons with emission lifetimes on nanosecond or microsecond timescales and triplet excitons with emission lifetimes on millisecond timescales appear simultaneously in different building blocks, with an efficient energy transfer process in the heterojunction. These organic materials also exhibit stimuli-responsive emission by changing the power or wavelength of the excitation laser. Potential applications of these organic heterostructures in integrated photonics, where the versatility of fluorescence, phosphorescence, efficient energy transfer, printability, and stimulus sensitivity co-exist in a single nanowire, are foreseen.

Elucidating Singlet-Fission-Born Multiexciton Dynamics via Molecular Engineering: A Dilution Principle Extended to Quintet Triplet Pair.

Multiexciton in singlet exciton fission represents a critical quantum state with significant implications for both solar cell applications and quantum information science. Two distinct fields of interest explore contrasting phenomena associated with the geminate triplet pair: one focusing on the persistence of long-lived correlation and the other emphasizing efficient decorrelation. Despite the pivotal nature of multiexciton processes, a comprehensive understanding of their dependence on the structural and spin properties of materials is currently lacking in experimental realizations. To address this gap in knowledge, molecular engineering was employed to modify the TIPS-tetracene structures, enabling an investigation of the structure-property relationships in spin-related multiexciton processes. In lieu of the time-resolved electron paramagnetic resonance technique, two time-resolved magneto-optical spectroscopies were implemented for quantitative analysis of spin-dependent multiexciton dynamics. The utilization of absorption and fluorescence signals as complementary optical readouts, in the presence of a magnetic field, provided crucial insights into geminate triplet pair dynamics. These insights encompassed the duration of multiexciton correlation and the involvement of the spin state in multiexciton decorrelation. Furthermore, simulations based on our kinetic models suggested a role for quintet dilution in multiexciton dynamics, surpassing the singlet dilution principle established by the Merrifield model. The integration of intricate model structures and time-resolved magneto-optical spectroscopies served to explicitly elucidate the interplay between structural and spin properties in multiexciton processes. This comprehensive approach not only contributes to the fundamental understanding of these processes but also aligns with and reinforces previous experimental studies of solid states and theoretical assessments.

Tert-butyl carbazole modified non-fused ring electron acceptor generating high triplet state energy level for efficient organic solar cell

Two-dimensional side-chain plays a crucial role in the construction of efficient non-fused ring electron acceptors (NFREAs). Herein, we introduce a novel NFREA, PCT-4Cl, featuring a tert-butyl carbazole side-chain, and investigate its optoelectronic properties. Notably, PCT-4Cl exhibits a small singlet-triplet energy gap (ΔEST) of 0.25 eV. Blending PCT-4Cl with host eC9 or C8C8–4Cl acceptor extends the lifetime of singlet excitons and exciton diffusion length in the blend films. Moreover, the high energy level of the triplet state (ET1) in PCT-4Cl facilitates efficient transfer of triplet excitons to eC9 or C8C8–4Cl. The addition of PCT-4Cl to PM6:eC9 also leads to a longer crystallization time, restraining eC9 aggregation and enhancing crystallinity in the ternary blend films. Consequently, power conversion efficiencies (PCEs) of 18.84 % and 15.17 % are achieved based on the optimized ternary devices of PM6:eC9:PCT-4Cl (1:1:0.2, wt./wt./wt.) and PM6:C8C8–4Cl:PCT-4Cl (1:1:0.2, wt./wt./wt.), respectively, surpassing the performance of PM6:eC9 (17.34 %) and PM6:C8C8–4Cl (14.05 %). Furthermore, leveraging 2PACz as a hole transporting layer elevates the PCEs of the ternary OSCs to 19.25 % and 15.53 %. These findings underscore the significant role of the tert-butyl carbazole side-chain in elevating the ET1 of NFREA for efficient charge transfer, as well as its role in modulating the crystallinity, presenting a promising pathway for achieving high performance in both binary and ternary OSCs.

A figure of merit for efficiency roll-off in TADF-based organic LEDs

Organic light-emitting diodes (OLEDs) are a revolutionary light-emitting display technology that has been successfully commercialized in mobile phones and televisions1,2. The injected charges form both singlet and triplet excitons, and for high efficiency it is important to enable triplets as well as singlets to emit light. At present, materials that harvest triplets by thermally activated delayed fluorescence (TADF) are a very active field of research as an alternative to phosphorescent emitters that usually use heavy metal atoms3,4. Although excellent progress has been made, in most TADF OLEDs there is a severe decrease of efficiency as the drive current is increased, known as efficiency roll-off. So far, much of the literature suggests that efficiency roll-off should be reduced by minimizing the energy difference between singlet and triplet excited states (ΔEST) to maximize the rate of conversion of triplets to singlets by means of reverse intersystem crossing (kRISC)5–20. We analyse the efficiency roll-off in a wide range of TADF OLEDs and find that neither of these parameters fully accounts for the reported efficiency roll-off. By considering the dynamic equilibrium between singlets and triplets in TADF materials, we propose a figure of merit for materials design to reduce efficiency roll-off and discuss its correlation with reported data of TADF OLEDs. Our new figure of merit will guide the design and development of TADF materials that can reduce efficiency roll-off. It will help improve the efficiency of TADF OLEDs at realistic display operating conditions and expand the use of TADF materials to applications that require high brightness, such as lighting, augmented reality and lasing.

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Oxygen vacancy regulating transition mode of MIL-125 to facilitate singlet oxygen generation for photocatalytic degradation of antibiotics

Efficient yield of 1O2 determines the photocatalytic degradation rate of antibiotics, but the regulatory mechanism for 1O2 selective generation in O2 activation is still lacking exploration. Herein, oxygen vacancy (OV) modification strategy of MIL-125 was successfully practiced to promote the selective generation of 1O2. Multiple characterizations including extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance spectra (EPR) confirmed the formation of oxygen vacancy in OV-MIL-125. The synthesized OV-MIL-125 exhibited greatly enhanced 1O2 selective (∼90 %) and antibiotics removal rate in water with high mineralization rate. Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence, transient absorption spectra (TAS) revealed that oxygen vacancy greatly enhanced the intersystem crossing (ISC) of singlet exciton, promoting triplet exciton generation. Density functional theoretical (DFT) calculation also proved the reduced gap of intersystem (ΔEST) and the modulated highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) population which was conducive to intersystem crossing process. Calculation of transition state further confirmed the lower energy barrier for π* orbital spin flip of O2 adsorbed on OV-MIL-125. The Dexter energy transfer involving triplet annihilation dominated the O2 activation mechanism to generate 1O2 instead of the charge transfer to generate O2•− which happened in MIL-125. This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.

Polaronic Stabilities of Exciton Sensitizers Govern Operational Lifetime of Thermally Activated Delayed Fluorescence Assisted Fluorescence Organic Light‐Emitting Devices

AbstractThermally activated delayed fluorescence (TADF) assisted fluorescence organic light‐emitting devices (TAF‐OLEDs), also known as hyperfluorescence OLEDs, sometimes have limited operational lifetimes, making them unsuitable for industrial applications. Although, this limitation is believed to originate from the irreversible degradation of constituent materials, the chemical processes underlying this degradation remain elusive. This study enables to better understand the chemical origins of the degradation processes by identifying key degradation intermediates in emission layers comprising 2,8‐di‐tert‐butyl‐5,11‐bis(4‐tert‐butylphenyl)‐6,12‐diphenyltetracene (TBRb) as the fluorescent emitter and 1,4‐azaborin‐based molecules exhibiting multi‐resonance (MR) TADF behaviors, 5,9‐diphenyl‐5,9‐diaza‐13b‐boranaphtho[3,2,1‐de]anthracene (DABNA‐1) and 9‐([1,1′‐biphenyl]‐3‐yl)‐N,N,5,11‐tetraphenyl‐5,9‐dihydro‐5,9‐diaza‐13b‐boranaphtho[3,2,1‐de]anthracen‐3‐amine (DABNA‐2), as exciton sensitizers. Despite the sensitizers facilitating energy transfer to TBRb, they also reduce the device's longevity. While the singlet and triplet excitons of TBRb, as well as excitons of the sensitizers, prove to be relatively stable, the radical ions of the sensitizers prove to be the key limit to device longevity. Comparisons with donor–acceptor‐type TADF exciton sensitizers, 2,4,5,6‐tetrakis(9H‐carbazol‐9‐yl)benzene‐1,3‐dicarbonitrile (4CzIPN), 10,10′‐(sulfonyldi‐4,1‐phenylene)bis[9,10‐dihydro‐9,9‐dimethylacridine] (DMAC‐DPS), and 10‐[4‐(4,6‐diphenyl‐1,3,5‐triazin‐2‐yl)phenyl]‐9,10‐dihydro‐9,9‐dimethylacridine (DMAC‐TRZ), corroborate the findings, pointing to radical ions as primary degradation intermediates. This knowledge is essential for enhancing the durability of TAF‐OLEDs in future designs.

Multi‐Responsive Thermally Activated Delayed Fluorescence Materials: Optical ZnCl2 Sensors and Efficient Green to Deep‐Red OLEDs

AbstractThermally activated delayed fluorescence (TADF) is an emission mechanism whereby both singlet and triplet excitons can be harvested to produce light. Significant attention is devoted to developing TADF materials for organic light‐emitting diodes (OLEDs), while their use in other organic electronics applications such as sensors, has lagged. A family of TADF emitters, TPAPyAP, TPAPyBP, and TPAPyBPN containing a triphenylamine (TPA) donor and differing nitrogen‐containing heterocyclic pyrazine‐based acceptors is developed and systematically studied. Depending on the acceptor strength, these three compounds emit with photoluminescence maxima (λPL), of 516, 550, and 575 nm in toluene. Notably, all three compounds show a strong and selective spectral response to the presence of ZnCl2, making them the first optical TADF sensors for this analyte. It is demonstrated that these three emitters can be used in vacuum‐deposited OLEDs, which show moderate efficiencies. Of note, the device with TPAPyBPN in 2,8‐bis(diphenyl‐phoshporyl)‐dibenzo[b,d]thiophene (PPT) host emits at 657 nm and shows a maximum external quantum efficiency (EQEmax) of 12.5%. This electroluminescence is significantly red‐shifted yet shows comparable efficiency compared to a device fabricated in 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl (CBP) host (λEL = 596 nm, EQEmax = 13.6%).

Dissociation of singlet excitons dominates photocurrent improvement in high-efficiency non-fullerene organic solar cells

Dissociation of singlet excitons dominates photocurrent improvement in high-efficiency non-fullerene organic solar cells

Asymmetric phosphorylation integrating host feature and blue thermally activated delayed fluorescence of thiaxanthene S,S-dioxide emitter for efficient heavily doped white organic light-emitting diodes

Significant efforts have been recently devoted to develop simply structured white organic light-emitting diodes (WOLEDs) based on purely thermally activated delayed fluorescence (TADF) with a single-emissive-layer and heavy-doping configuration. Herein, through introducing a diphenylphosphine oxide group on thiaxanthene S,S-dioxide acceptor, we integrate host characteristics to blue TADF emitter CZ-MPSPO, which is beneficial to balanced exciton allocation and quenching suppression in single emissive layers of TADF WOLEDs for high performance. After co-doping with a conventional yellow TADF emitter, TADF performance of CZ-MPSPO is preserved, but external quantum efficiencies (EQE) of WOLEDs are remarkably improved through the synergistic singlet and triplet exciton harvesting by CZ-MPSPO and 4CzTPNBu. The steric hindrance of CZ-MPSPO also mitigates emission quenching by 4CzTPNBu, leading to the favourable EQE up to ∼20 % of single-EML pure TADF WOLEDs with the doping concentration of CZ-MPSPO as high as 70 %.

TADF polymer enables over 20% EQE in solution‐processed green fluorescent OLEDs

AbstractSolution‐processed fluorescent organic light‐emitting diodes (OLEDs) are believed to be favorable for low‐cost, large‐area, and flexible displays but still suffer from the limited external quantum efficiency (EQE) below 5%. Herein, we demonstrate the EQE breakthrough by introducing a donor–acceptor type thermally activated delayed fluorescence (TADF) polymer as the sensitizer for the typical green‐emitting fluorescent dopants. Benefitting from their matched energy alignment, the unwanted trap‐assisted recombination directly on fluorescent dopant is prevented to avoid the additional loss of triplet excitons. Indeed, triplet excitons are mainly formed on the polymeric TADF sensitizer via a Langevin recombination and then spin‐flipped to singlet excitons due to the good upconversion capability. Followed by an efficient Förster energy transfer, both singlet and triplet excitons can be harvested by fluorescent dopants, leading to a promising solution‐processed green hyperfluorescence with a record‐high EQE of 21.2% (72.2 cd/A, 59.7 lm/W) and Commission Internationale de L'Eclairage coordinates of (0.32, 0.59). The results clearly highlight the great potential of solution‐processed fluorescent OLEDs based on TADF polymers as the sensitizer.

Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low‐Threshold Laser to Room‐temperature Phosphorescence in Amorphous‐Film for Highly Efficient OLEDs

AbstractMetal‐organic phosphorescent complexes containing Ir or Pt are work horse in organic light‐emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy‐atom effect. Recently, organic room‐temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal‐organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin‐films, based on a tert‐butylcarbazole difluoroboron β‐diketonate derivative of DtCzBF2. Tightly packed and well‐faceted single‐crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm−1. In contrast, loosely packed dimers of DtCzBF2 formed in guest‐host amorphous thin‐films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution‐processed OLEDs with EQE approaching 20 %. This study opens possibilities of low‐cost ORTP emitters for high performance OLEDs and future low‐threshold electrically injected organic semiconductor lasers (OSLs).

Switching from Thermally Activated Delayed Fluorescence in Single Crystals for Low-Threshold Laser to Room-temperature Phosphorescence in Amorphous-Film for Highly Efficient OLEDs.

Metal-organic phosphorescent complexes containing Ir or Pt are work horse in organic light-emitting diode (OLED) technology, which can harvest both singlet and triplet excitons in electroluminescence (EL) owing to strong heavy-atom effect. Recently, organic room-temperature phosphorescence (ORTP) have achieved high photoluminescence quantum yield (PLQY) in rigid crystalline state, which, however, is unsuitable for OLED fabrication, therefore leading to an EL efficiency far low behind those of metal-organic phosphorescent complexes. Here, we reported a luminescence mechanism switch from thermally activated delayed fluorescence (TADF) in single crystal microwires to ORTP in amorphous thin-films, based on a tert-butylcarbazole difluoroboron β-diketonate derivative of DtCzBF2. Tightly packed and well-faceted single-crystal microwires exhibit aggregation induced emission (AIE), enabling TADF microlasers at 473 nm with an optical gain coefficient as high as 852 cm-1 . In contrast, loosely packed dimers of DtCzBF2 formed in guest-host amorphous thin-films decrease the oscillator strength of fluorescence transition but stabilize triplets for ORTP with a PLQY up to 61 %, leading to solution-processed OLEDs with EQE approaching 20 %. This study opens possibilities of low-cost ORTP emitters for high performance OLEDs and future low-threshold electrically injected organic semiconductor lasers (OSLs).

Correction to “On the Role of Nuclear Motion in Singlet Exciton Fission: The Case of Single‐Crystal Pentacene”

Correction to “On the Role of Nuclear Motion in Singlet Exciton Fission: The Case of Single‐Crystal Pentacene”

Sn-fused perylene diimides: Synthesis, mechanism, and properties

The first example of metal Sn-fused perylene diimides (PDI) derivative (Sn-PDI) was designed, synthesized, and investigated. To obtain this type compound, a simple one-pot synthesis, named stannylative cycloaddition reaction, has been successfully developed via a palladium-based catalyst system. The novel mechanism exhibits that the reaction experiences oxidative addition, Pd-cyclization, stannylation, Pd-Sn-cyclization, and reductive elimination processes successively. This stannylative cycloaddition does realize unique σ-π hyperconjugation effect and therefore significantly influencing on the photophysical, electrochemical and excited state properties. Compared with those of PDI, both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm. The electron energy levels of Sn-PDI have changed with an uncommon regulation. And Sn-PDI gives a considerably raised highest occupied molecular orbital (HOMO) level of -6.00 eV More importantly, the singlet excitons of Sn-PDI could efficiently intersystem cross (ISC) into triplet state with a long lifetime of 17.8 µs, which is far longer than that (4.4 ns) of PDI.

On the critical competition between singlet exciton decay and free charge generation in non-fullerene based organic solar cells with low energetic offsets.

Reducing voltage losses while maintaining high photocurrents is the holy grail of current research on non-fullerene acceptor (NFA) based organic solar cell. Recent focus lies in understanding the various fundamental mechanisms in organic blends with minimal energy offsets - particularly the relationship between ionization energy offset (ΔIE) and free charge generation. Here, we quantitatively probe this relationship in multiple NFA-based blends by mixing Y-series NFAs with PM6 of different molecular weights, covering a broad power conversion efficiency (PCE) range: from 15% down to 1%. Spectroelectrochemistry reveals that a ΔIE of more than 0.3 eV is necessary for efficient photocurrent generation. Bias-dependent time-delayed collection experiments reveal a very pronounced field-dependence of free charge generation for small ΔIE blends, which is mirrored by a strong and simultaneous field-dependence of the quantified photoluminescence from the NFA local singlet exciton (LE). We find that the decay of singlet excitons is the primary competition to free charge generation in low-offset NFA-based organic solar cells, with neither noticeable losses from charge-transfer (CT) decay nor evidence for LE-CT hybridization. In agreement with this conclusion, transient absorption spectroscopy consistently reveals that a smaller ΔIE slows the NFA exciton dissociation into free charges, albeit restorable by an electric field. Our experimental data align with Marcus theory calculations, supported by density functional theory simulations, for zero-field free charge generation and exciton decay efficiencies. We conclude that efficient photocurrent generation generally requires that the CT state is located below the LE, but that this restriction is lifted in systems with a small reorganization energy for charge transfer.

Anthracene derivatives with strong spin-orbit coupling and efficient high-lying reverse intersystem crossing beyond the El-Sayed rule.

The attention to materials with hot exciton channel and triplet-triplet fusion (TTF) mediated high-lying reverse intersystem crossing (hRISC) has been raised for their ability to convert non-emissive 'dark' triplets into radiative singlet excitons. This spin conversion process results in high exciton utilization efficiency (EUE) that exceeds the theoretical limits. Notably, it is known that such spin conversion processes from the high-lying excited triplet to the singlet state are facilitated by the orthogonal orbital transition effect governed by the El-Sayed's rule. In this study, an anthracene derivative with indenoquinoline substituent 7,7-dimethyl-9-(10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)-7H-indeno[1,2-f]quinoline (2MIQ-NPA) was synthesized and analyzed to investigate whether the hRISC process occurs in these molecules, even when the El-Sayed's rule is not followed. The hRISC channels of the emitter were fully unraveled through DFT calculations and experiments, which were quantitatively subdivided using transient electroluminescence measurements. The results showed that 2MIQ-NPA, which does not follow the El-Sayed's rule and has a relatively strong spin-orbit coupling matrix element of 0.116 cm-1 between the high-lying triplet state of T4 and the lowest singlet state of S1, effectively converted triplet excitons into singlet excitons with an EUE of 64.3%, contributed by a direct hot exciton channel of 19.2% and a TTF-mediated hot exciton channel of 15.1%. Despite the low outcoupling efficiency, the non-doped device with 2MIQ-NPA achieved an excellent device performance with an external quantum efficiency of 7.0%.

Singlet fission in TIPS-anthracene thin films.

Singlet fission is an exciton multiplication process that allows for the conversion of one singlet exciton into two triplet excitons. Organic semiconductors, such as acenes and their soluble bis(triisopropylsilylethynyl) (TIPS) substituted counterparts, have played a major role in elucidating the understanding of the underlying mechanisms of singlet fission. Despite this, one prominent member of the acene family that has received little experimental attention to date is TIPS-anthracene, even with computational studies suggesting potential high singlet fission yields in the solid state. Here, time-resolved spectroscopic and magneto-photoluminescence measurements were performed on spin-cast films of TIPS-anthracene, showing evidence for singlet fission. A singlet fission yield of 19% (out of 200%) is estimated from transient absorption spectroscopy. Kinetic modeling of the magnetic field effect on photoluminescence suggests that fast rates of triplet dissociation lead to a low magnetic photoluminescence effect and that non-radiative decay of both the S1 and 1(TT) states is the cause for the low triplet yield.

Tunable electrochemiluminescence of TADF luminophores: manipulating efficiency and unveiling water-soluble emitters.

Thermally Activated Delayed Fluorescent (TADF) luminophores offer the potential to achieve 100% Internal Quantum Efficiency (IQE) by harvesting both singlet and triplet excitons via reverse intersystem crossing from T1 to S1. This class of molecules has therefore been embraced in the pursuit of cheaper and more efficient electrochemiluminescent (ECL) labels. The present study explores how tuning the electron-donating (D) and -accepting (A) strengths of peripheral substituents affects the ECL emission of mono- and dicyanoarene-based TADF dyes. To this end, we synthesized two series of TADF compounds, independently manipulating electron donors and acceptors by (i) halogenating electron-rich diphenylamine moieties, or (ii) mono- or di-substituting the electron-poor cyanoarene core with either fluorine or imidazole. Through a comparative analysis, we elucidate the role of each substituent in shaping the photophysics of the investigated luminophores. Despite only achieving a relative Φ ECL as high as 1.27%, this framework identifies several molecular features that boost the ECL efficiency to pave the way for designing highly efficient TADF-based ECL emitters. Ultimately, imidazole substituents are exploited as a platform for functionalization with triethylene glycol units. The resulting water-soluble TADF luminophores are characterized under conditions usual to commercial ECL bioanalysis, proving their potential as a cost-effective alternative replacement to [Ru(bpy)3]2+ in clinical diagnostic.

Decorrelated singlet and triplet exciton delocalization in acetylene-bridged Zn-porphyrin dimers.

The controlled delocalization of molecular excitons remains an important goal towards the application of organic chromophores in processes ranging from light-initiated chemical transformations to classical and quantum information processing. In this study, we present a methodology to couple optical and magnetic spectroscopic techniques and assess the delocalization of singlet and triplet excitons in model molecular chromophores. By comparing the steady-state and time-resolved optical spectra of Zn-porphyrin monomers and weakly coupled dimers, we show that we can use the identity of substituents bound at specific positions of the macromolecules' rings to control the inter-ring delocalization of singlet excitons stemming from their B states through acetylene bridges. While broadened steady-state absorption spectra suggest the presence of delocalized B state excitons in mesityl-substituted Zn-tetraphenyl porphyrin dimers (Zn2U-D), we confirm this conclusion by measuring an enhanced ultrafast non-radiative relaxation from these inter-ring excitonic states to lower lying electronic states relative to their monomer. In contrast to the delocalized nature of singlet excitons, we use time-resolved EPR and ENDOR spectroscopies to show that the triplet states of the Zn-porphyrin dimers remain localized on one of the two macrocyclic sub-units. We use the analysis of EPR and ENDOR measurements on unmetallated model porphyrin monomers and dimers to support this conclusion. The results of DFT calculations also support the interpretation of localized triplet states. These results demonstrate researchers cannot conclude triplet excitons delocalize in macromolecular based on the presence of spatially extended singlet excitons, which can help in the design of chromophores for application in spin conversion and information processing technologies.