Singlet Ground State Research Articles

Dicyclopenta[4,3,2,1‐cde:4′,3′,2′,1′‐pqr]‐peri‐tetracene: Synthesis and an Example of Annulene‐within‐an‐Annulene Aromaticity in Different Redox States

AbstractWe report a robust strategy for tuning the electronic structure and chemical stability of π‐conjugated polycyclic hydrocarbons (PHs). By fusing two cyclopentadienyl rings in the peri‐tetracene bay regions, we introduce antiaromatic character into the π‐system, leading to unique photophysical and electronic properties. A stable mesityl‐substituted dicyclopenta‐peri‐tetracene derivative was synthesized through stepwise formylation/intramolecular cyclization at the bay regions of the dihydro peri‐tetracene precursor, followed by oxidative dehydrogenation. This compound features an open‐shell singlet diradical ground state, global antiaromaticity, exceptional stability under ambient conditions, and amphoteric redox behavior with a small energy gap. Its dication also possesses an open‐shell singlet ground state, and its structure was identified by X‐ray crystallographic analysis, revealing a unique [14]annulene‐within‐[22]annulene global aromatic structure. In contrast, the dianion exhibits a closed‐shell singlet ground state. This work provides valuable insights for designing and synthesizing novel open‐shell PHs with tunable electronic structures and remarkable stability.

Photochemical and Sono-Photochemical Studies of Zn (II) Porphyrin-conjugated Chitosan Hydrogels for Enhanced Singlet Oxygen Generation

This study explores the synthesis, characterization, photochemical, and sono-photochemical properties of covalently conjugated porphyrin-chitosan hydrogels for potential application in photodynamic therapy (PDT) and sono-photodynamic therapy (SPDT). The efficient production of singlet oxygen, a crucial reactive oxygen species (ROS) in these therapies, was investigated. Zinc(II) porphyrins 1 and 2 were synthesized by metal insertion to free based porphyrins and covalently linked to chitosan via Schiff-base reaction to produce chitosan hydrogel CS-1 and CS-2 (conjugation via phenylacetylene spacer). The synthesized compounds were characterized using standard spectroscopic techniques, confirming successful conjugation. Scanning electron microscopy (SEM) analysis demonstrating the homogeneous distribution of porphyrins within the hydrogel matrix. Photophysical and photochemical properties, including ground state absorption and singlet oxygen generation, were evaluated for both porphyrin complexes and chitosan-conjugated hydrogels in DMSO. The porphyrin-hydrogel structures showed superior singlet oxygen generation efficiency. Sono-photochemical studies showed further enhanced singlet oxygen generation, with the highest quantum yield (ΦΔ= 0.81) observed for the chitosan hydrogel CS-2. The results demonstrated enhanced singlet oxygen generation in the hydrogel structures, particularly under simultaneous ultrasound and light irradiation, indicating their potential efficacy in PDT and SPDT applications. Additionally, photo degradation studies revealed the stability of the synthesized compounds under light irradiation. These findings highlight the potential of porphyrin-conjugated chitosan hydrogels as effective photosensitizers for PDT and SPDT applications.

Synthesis, Structural Aspects, Magnetic, and Adsorption Properties of a Dinuclear Cu (II) Complex Derived From Mixed Ligand Approach

ABSTRACTA dinuclear copper complex, [Cu2(teaH)(pNBA)2(H2O)2]·MeOH·pNBH (1) (where teaH3 = triethanolamine, pNBH = 4‐nitro‐benzoic acid, and pNBA = 4‐nitro‐benzoate) has been prepared and structurally characterized. In 1, there is an interesting intermolecular structure that is shown as a tetramer copper connected in chain‐like motif. In the UV‐Vis spectrum, higher absorbance at 267 nm is referred to n → π* transition, coupled with a weak peak at 500 nm, indicating another transition, which is specified as metal‐to‐ligand charge transfer. The higher intensity peak in the photoluminescence spectrum is marked as the absorption of energy required for the excitation of electrons, whereas lower intensity peaks show the emission of energy, which describes d‐d transitions of Cu (II) electrons due to d9 configuration. Complex 1 was explored for the adsorption of methylene blue (MB) dye, with the maximum adsorption as 101.07 mg/g, whereas the removal efficiency was estimated to be 81.05%. In conformity with the kinetic studies, the adsorption process proceeded via a Pseudo‐first‐order kinetic model. The incorporation of mixed ligands such as teaH3 and pNBH in 1 tends to increase the dimensionality that led to increased MB adsorption. The plausible mechanism behind the adsorption was favored by hydrogen‐bonding, electrostatic, π–π, and n–π* interactions, operating between the dye and complex 1. Further, the H‐bonding and these interactions provided stability to the complex, and an improved dye adsorption was observed even during the 2nd and 3rd recyclability experiments. Additionally, complex 1 corroborated remarkable stability after dye adsorption, allowing for up to four recycling turns. The magnetic study revealed antiferromagnetic coupling between the two magnetic centers with a singlet ground state (S = 0).

Frustrated Radical Pairs: From Fleeting Intermediates to Isolable Species.

We present the design and comprehensive investigation of stable para-substituted triarylamine-2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) radical ion pairs (RIPs) generated via single-electron transfer (SET). We quantified the degree of SET in both solution and solid phases, utilising a suite of spectroscopic techniques including IR, EPR, NMR, and single-crystal X-ray diffraction (SC-XRD). Our findings reveal that the extent of SET is significantly influenced by the nature of the substituents (MeO > tBu > Br) and the polarity of the solvent (MeCN > DCM > toluene). The radical ion pair [(pMeOPh)3N]•+[DDQ]•- was unambiguously identified using EPR and UV-vis spectroscopy, and its structure was confirmed by SC-XRD. Detailed analysis indicates an open-shell singlet ground state with a thermally accessible triplet state, as corroborated by EPR, magnetic susceptibility measurements, and DFT calculations. This study offers crucial insights into the mechanistic pathways of RIP formation and tuning both in solution and solid states, laying the groundwork for future exploration of their reactivity and potential applications.

Rational Design of Crystalline and Enantiomerically Pure Helicenes with Open‐Shell Singlet Ground States

AbstractHelicene diradical derivatives have attracted widespread attentions because of their unique magnetic and chiroptoelectronic properties, however, crystalline and enantiomerically pure forms of helicene diradicals are extremely rare. Herein, we describe the rational design and synthesis of o‐quinone functionalized helicene diradicals with crystalline enantiomerical purity. Diradical dianion salt Rac‐3K and its enantiomers P/M‐3K were obtained by reduction of corresponding precursors Rac‐3 and P/M‐3 with two equivalent potassium graphite in THF in the presence of (di)benzo‐18‐crown‐6. Neutral dioxoborocyclic helicene diradicals (Rac‐3B and P/M‐3B) were produced by reactions of Rac‐3 or P/M‐3 with chlorobis(perfluorophenyl)borane (B(C6F5)2Cl. Crystal structures of compounds Rac‐3K, Rac‐3B and P/M‐3K were obtained by single crystal X‐ray diffraction. Their open‐shell singlet state ground states were confirmed by electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) measurements and theoretical calculations. Their chiroptical properties were investigated by the electronic circular dichroism (ECD) spectroscopy. This work provides the first examples of enantiopure helicene diradical dianions and boron‐containing helicene diradicals.

Dicyclopenta[4,3,2,1-cde:4',3',2',1'-pqr]-peri-tetracene: Synthesis and An Example of Annulene-Within-An-Annulene Aromaticity in Different Redox States.

We report a robust strategy for tuning the electronic structure and chemical stability of π-conjugated polycyclic hydrocarbons (PHs). By fusing two cyclopentadienyl rings in the peri-tetracene bay regions, we introduce antiaromatic character into the π-system, leading to unique photophysical and electronic properties. A stable mesityl-substituted dicyclopenta-peri-tetracene derivative was synthesized through stepwise formylation/intramolecular cyclization at the bay regions of the dihydro peri-tetracene precursor, followed by oxidative dehydrogenation. This compound features an open-shell singlet diradical ground state, global antiaromaticity, exceptional stability under ambient conditions, and amphoteric redox behavior with a small energy gap. Its dication also possesses an open-shell singlet ground state, and its structure was identified by X-ray crystallographic analysis, revealing a unique [14]annulene-within-[22]annulene global aromatic structure. In contrast, the dianion exhibits a closed-shell singlet ground state. This work provides valuable insights for designing and synthesizing novel open-shell PHs with tunable electronic structures and remarkable stability.

Rational Design of Crystalline and Enantiomerically Pure Helicenes with Open-Shell Singlet Ground States.

Helicene diradical derivatives have attracted widespread attentions because of their unique magnetic and chiroptoelectronic properties, however, crystalline and enantiomerically pure forms of helicene diradicals are extremely rare. Herein, we describe the rational design and synthesis of o-quinone functionalized helicene diradicals with crystalline enantiomerical purity. Diradical dianion salt Rac-3K and its enantiomers P/M-3K were obtained by reduction of corresponding precursors Rac-3 and P/M-3 with two equivalent potassium graphite in THF in the presence of (di)benzo-18-crown-6. Neutral dioxoborocyclic helicene diradicals (Rac-3B and P/M-3B) were produced by reactions of Rac-3 or P/M-3 with chlorobis(perfluorophenyl)borane (B(C6F5)2Cl. Crystal structures of compounds Rac-3K, Rac-3B and P/M-3K were obtained by single crystal X-ray diffraction. Their open-shell singlet state ground states were confirmed by electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) measurements and theoretical calculations. Their chiroptical properties were investigated by the electronic circular dichroism (ECD) spectroscopy. This work provides the first examples of enantiopure helicene diradical dianions and boron-containing helicene diradicals.

Block-Correlated Coupled Cluster Theory Based on the Generalized Valence Bond Reference for Singlet-Triplet Energy Gaps of Strongly Correlated Systems.

A block-correlated coupled cluster (BCCC) method based on the triplet generalized valence bond (GVB) wave function (GVB-BCCC) has been implemented for the first time. By introducing several techniques, we have developed a practical and efficient GVB-BCCC code. The GVB-BCCC3 method (with up to three-pair correlation) can be used to deal with strongly correlated (SC) systems with triplet or singlet ground states, allowing singlet-triplet (S-T) energy gaps in the active space of SC systems computationally available. For selected SC systems, our calculations show that GVB-BCCC3 can always provide correct ground-state spin multiplicity as the complete active space configuration interaction (CASCI) or density matrix renormalization group (DMRG). Furthermore, we found that the S-T energy gaps from GVB-BCCC3 are quite consistent with CASCI or DMRG results. This work demonstrates that GVB-BCCC3 is a promising theoretical tool for describing S-T energy gaps within the active space of SC systems with large active spaces.

Dibenzo-peri-Heptacene: A Stable Open-Shell Graphene Fragment With a Balanced Combination of Armchair and Zigzag Edge Structures.

Atomically precise open-shell graphene fragments, such as extended peri-acenes, hold significant interest for electronics and spintronics. However, their inherent high reactivity poses challenges for synthesis and application. In this study, a novel approach is introduced: the fusion of a zigzag-edged peri-tetracene with an all-armchair-edged hexa-peri-hexabenzocoronene (HBC) via two shared benzene rings to produce a stable open-shell hydrocarbon, named dibenzo-peri-heptacene (DBPH). The DBPH derivative 1 exhibits considerably enhanced stability, with a half-life (t1/2) of 46 days in toluene solution under ambient conditions. This improved stability is attributed to peri-benzannulation, enhanced aromatic stabilization, and kinetic protection of the reactive sites along the zigzag edges. The structure of 1 is unequivocally verified through single-crystal X-ray diffraction analysis. With a balanced combination of armchair and zigzag edge structures, derivative 1 displays a diradical character of 39.2% and a singlet-triplet gap of ≈-3.16 kcalmol-1. It features a narrow electrochemical energy gap (0.87 eV) and exhibits amphoteric redox behavior. Notably, its dication and dianion states manifest a closed-shell singlet ground state, representing doubly charged structures where a HBC unit is fused with a benzo[f]tetraphene moiety. This research paves the way for synthesizing novel open-shell graphene fragments with adjustable electronic properties and exceptional stability.

N-Carbazolyl π-Radical and Its Antiaromatic Nitrenium Ion: A Threshold Photoelectron Spectroscopic Study.

Understanding the structure and properties of heterocyclic radicals and their cations is crucial for elucidating reaction mechanisms as they serve as versatile synthetic intermediates. In this work, the N-carbazolyl radical 1 was generated via pyrolysis and characterized using photoion mass-selected threshold photoelectron spectroscopy coupled with tunable vacuum-ultraviolet synchrotron radiation. The N-centered radical 1 is classified as a π-radical (2B1), with the unpaired electron found to be delocalized over the central five-membered ring of the carbazole. Adiabatic ionization energies corresponding to the transition from radical 1 to its singlet 1+(1A1) and triplet 1+(3B2) cations were determined to be 7.70 ± 0.03 and 8.14 ± 0.03 eV, respectively. The antiaromatic nitrenium ion 1+ exhibits a singlet ground state with an experimental singlet-triplet energy gap (ΔES-T) of -0.44 eV (10.1 kcal/mol), in very good agreement with theory. N-centered radicals are found to have a higher ionization energy than their C-centered analogues due to stabilization of the singly occupied molecular orbital.

Azaacene Diradicals Based on Non-Kekulé Meta-Quinodimethane with Large Two-Photon Cross-Sections in the Infrared Spectral Region.

Non-Kekulé quinoidal azaacences m-A (1 a,b) were synthesized and compared to their para- and ortho-quinodimethane analogues. m-A display high diradical characters (1 b: y0 = 0.88) due to their meta-quinodimethane (m-QDM) topology. Electron paramagnetic, nuclear magnetic resonance spectroscopies and supraquantum interference device measurements in combination with quantum-chemical calculations revealed singlet ground states for m-A with singlet-triplet gaps ΔEST (0.13-0.25 kcal mol-1) and thermally populated triplet states. These non-Kekulé structures are over all void of zwitterionic character and possess record high two-photon absorption cross sections over a broad spectral range in the near-infrared.

Azaacene Diradicals Based on Non‐Kekulé Meta‐Quinodimethane with Large Two‐Photon Cross‐Sections in the Infrared Spectral Region

AbstractNon‐Kekulé quinoidal azaacences m‐A (1 a,b) were synthesized and compared to their para‐ and ortho‐quinodimethane analogues. m‐A display high diradical characters (1 b: y0 = 0.88) due to their meta‐quinodimethane (m‐QDM) topology. Electron paramagnetic, nuclear magnetic resonance spectroscopies and supraquantum interference device measurements in combination with quantum‐chemical calculations revealed singlet ground states for m‐A with singlet‐triplet gaps ΔEST (0.13–0.25 kcal mol−1) and thermally populated triplet states. These non‐Kekulé structures are over all void of zwitterionic character and possess record high two‐photon absorption cross sections over a broad spectral range in the near‐infrared.

Oxygen-doped Carbon Nitrides with Visible Room-temperature Phosphorescence and Invisible Thermal-Stimuli-Responsive Ultraviolet Delayed Fluorescence for Security Applications.

Multi-mode emissive materials with stimuli-responsive producing invisible signals are very attractive for advanced security applications, but development of such materials remains highly challenging. In this work, oxygen-doped carbon nitrides (O-CNs) are prepared via microwave-assisted heating of urea, which exhibit ultraviolet (UV) solid-state fluorescence (SSFL), visible room temperature phosphorescence (RTP) and thermal-stimuli production of invisible UV delayed fluorescence (DF) properties. Further studies confirmed that the SSFL and RTP could be attributed to the introduction of oxygen functional group (e. g., C=O) in the skeleton of O-CNs, thus minimizing the aggregation caused quenching effect, facilitating intersystem crossing, and stabilizing the excited triplet states. The specific thermal-stimuli production of UV DF is deemed to be the relatively large energy gap between ground and excited singlet states as well as an effective triplet-triplet annihilation. Notably, the emission maximum of UV DF locates at ~310 nm with an ultra-narrow full width at half maximum (FWHM) down to 19 nm, so it is completely invisible to the naked eyes, but detectable by a UV camera. To employ the unique characteristics of O-CNs, security protection strategies with superior concealment by virtue of the thermal-stimuli quenching visible RTP and meanwhile producing invisible UV DF are demonstrated.

Oxygen‐doped Carbon Nitrides with Visible Room‐temperature Phosphorescence and Invisible Thermal‐Stimuli‐Responsive Ultraviolet Delayed Fluorescence for Security Applications

AbstractMulti‐mode emissive materials with stimuli‐responsive producing invisible signals are very attractive for advanced security applications, but development of such materials remains highly challenging. In this work, oxygen‐doped carbon nitrides (O‐CNs) are prepared via microwave‐assisted heating of urea, which exhibit ultraviolet (UV) solid‐state fluorescence (SSFL), visible room temperature phosphorescence (RTP) and thermal‐stimuli production of invisible UV delayed fluorescence (DF) properties. Further studies confirmed that the SSFL and RTP could be attributed to the introduction of oxygen functional group (e. g., C=O) in the skeleton of O‐CNs, thus minimizing the aggregation caused quenching effect, facilitating intersystem crossing, and stabilizing the excited triplet states. The specific thermal‐stimuli production of UV DF is deemed to be the relatively large energy gap between ground and excited singlet states as well as an effective triplet‐triplet annihilation. Notably, the emission maximum of UV DF locates at ~310 nm with an ultra‐narrow full width at half maximum (FWHM) down to 19 nm, so it is completely invisible to the naked eyes, but detectable by a UV camera. To employ the unique characteristics of O‐CNs, security protection strategies with superior concealment by virtue of the thermal‐stimuli quenching visible RTP and meanwhile producing invisible UV DF are demonstrated.

Non-Kekulé meta-Quinodimethane Singlet Diradicals Based on Classical N-Heterocyclic Carbenes.

Diradicals based on a meta-quinodimethane (m-QDM) scaffold generally have a triplet ground state and are rather scarce. Herein, m-QDM-based non-Kekulé diradicals [3,3'-(NHC)2BP] (3-NHC) (NHC = SIPr = C{N(Dipp)CH2}2; IPr = C{N(Dipp)CH}2, Me-IPr = C{N(Dipp)CMe}2; Dipp = 2,6-iPr2C6H3; BP = 1,1'-C6H4C6H4) featuring N-heterocyclic carbene (NHC) pendants are reported as crystalline solids. The EPR spectra of 3-NHC show both allowed (Δms = 1) and forbidden (Δms = 2; 'half-field') transitions characteristic for triplet diradicals. Variable temperature EPR studies however reveal a singlet ground state for 3-SIPr. Consistent with the EPR spectra, calculations predict a remarkably small singlet-triplet energy gap (ΔEST ≤ 0.26 kcal/mol) for the 3-NHC compounds. The calculated singlet diradical character for the ground states of the 3-NHC compounds amounts to ~99 %.

Preparation and Ground-State Electronic Structure of Heterobimetallic Yb-PtIV-Alkyl Complexes.

This article focuses on the synthesis of heterobimetallic complexes of lanthanide and platinum. It describes the synthesis of the Cp*Yb(bipym)PtMe2 complex and its characterization, followed by its reactivity with oxidants, giving access to various Pt + IV compounds of trismethyl (PtMe3) and tetramethyl (PtMe4) fragments. Characterization of the electronic properties of the complexes by magnetic measurements demonstrated that the tetramethyl complex possesses a singlet ground state. The trismethyl fragments, on the other hand, have a ground state that evolves as a function of the ligand saturating the coordination sphere: a singlet for triflate and pyridine and a triplet for iodine, demonstrating the capacity for simple tuning of the electronic structure of these complexes. While the addition of B(C6F5)3 to the platinum + II bis methyl complex leads to FLP-like reactivity triggering THF opening, reactivity with [Ph3C]+[BPh4]- leads to oxidation of the bipym ligand. Furthermore, the light reactivity of the tetramethyl complex indicated the possible transfer of a methyl group, leading to functionalization of the bridging bipym ligand.

Direct Photopatterning of Colloidal Quantum Dots with Electronically Optimized Diazirine Cross-Linkers.

Colloidal quantum dots (QDs) with a wide color gamut and high luminescent efficiency are promising for next-generation electronic and photonic devices. However, precise and scalable patterning of QDs without degrading their properties and their integration into commercially relevant devices, such as digitally addressable QD light-emitting diode (QLED) displays, remain challenging. Here, we develop electronically optimized diazirine-based cross-linkers for nondestructive, direct photopatterning of QDs and, ultimately, building the active-matrix QLED displays. The key to the cross-linker design is the introduction of electron-donating substituents that permit the formation of ground-state singlet carbenes for air-stable and benign QD photopatterning. Under ambient conditions, these cross-linkers enable the patterning of heavy metal-free QDs at a resolution of over 13,000 pixels per inch using commercial i-line photolithography. The patterned QD layers fully preserved their optical and optoelectronic properties. Pixelated electroluminescent devices with patterned InP/ZnSe/ZnS QD layers show a peak external quantum efficiency of 15.3% and a maximum luminance of about 40,000 cd m-2, outperforming those made by existing QD patterning approaches. We further show the seamless integration of patterned QLEDs with thin-film transistor circuits and the fabrication of dual-color active-matrix displays. These results underscore the importance of designing photochemistry for QD patterning, and promise the implementation of direct photopatterning methods in manufacturing commercial QLED displays and other integrated QD device platforms.

N-Heterocyclic Carbene-Derived Carbon Disulfide Radical Ligands for Palladium Diradicals.

N-heterocyclic carbenes (NHCs) are recognized for their ability to stabilize various main group radicals; however, NHC-derived, sulfur-based radicals remain rare. In this study, we successfully synthesized and characterized a series of palladium diradical complexes that featured new sulfur-based radical ligands from NHC-carbon disulfide adducts. Spectroscopic and computational characterizations of the palladium complexes confirmed the open-shell singlet ground state, which resulted from the antiferromagnetic coupling of two unpaired electrons on each ligand. Proton nuclear magnetic resonance relaxometry was used to experimentally confirm the presence of these unpaired electrons. Moreover, the redox behavior of the complexes was localized on the ligand center, confirming the redox activity of the ligands. The discovery of this sulfur-based, redox-active radical ligand underscores the versatility and significance of NHC-derived radicals, thereby expanding the repertoire of radical ligands and opening new avenues for advanced material and catalytic systems.

Tuning the Spin Interaction in Nonplanar Organic Diradicals through Mechanical Manipulation.

Open-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhibit spin delocalization, form extended collective states, and respond to the flexibility of the molecular backbones. However, they are also highly reactive, requiring structural strategies to protect the radical states from reacting with the environment. Here, we demonstrate that the open-shell ground state of the diradical 2-OS survives on a Au(111) substrate as a global singlet formed by two unpaired electrons with antiparallel spins coupled through a conformational-dependent interaction. The 2-OS molecule is a "protected" derivative of the Chichibabin's diradical, featuring a nonplanar geometry that destabilizes the closed-shell quinoidal structure. Using scanning tunneling microscopy (STM), we localized the two interacting spins at the molecular edges, and detected an excited triplet state a few millielectronvolts above the singlet ground state. Mean-field Hubbard simulations reveal that the exchange coupling between the two spins strongly depends on the torsional angles between the different molecular moieties, suggesting the possibility of influencing the molecule's magnetic state through structural changes. This was demonstrated here using the STM tip to manipulate the molecular conformation, while simultaneously detecting changes in the spin excitation spectrum. Our work suggests the potential of these PAHs as all-carbon spin-crossover materials.

On‐Surface Synthesis of Triaza[5]triangulene through Cyclodehydrogenation and its Magnetism

AbstractTriangulenes as neutral radicals are becoming promising candidates for future applications such as spintronics and quantum technologies. To extend the potential of the advanced materials, it is of importance to control their electronic and magnetic properties by multiple graphitic nitrogen doping. Here, we synthesize triaza[5]triangulene on Au(111) by cyclodehydrogenation, and its derivatives by cleaving C−N bonds. Bond‐resolved scanning tunneling microscopy and scanning tunneling spectroscopy provided detailed structural information and evidence for open‐shell singlet ground state. The antiferromagnetic arrangement of the spins in positively doped triaza[5]triangulene was further confirmed by density function theory calculations. The key aspect of triangulenes with multiple graphitic nitrogen is the extra pz electrons composing the π orbitals, favoring charge transfer to the substrate and changing their low‐energy excitations. Our findings pave the way for the exploration of exotic low‐dimensional quantum phases of matter in heteroatom doped organic systems.