Potent Electron Acceptor Research Articles

Bisphosphonium Benzene Diimides.

The incorporation of cationic groups onto electron-poor compounds is a viable strategy for achieving potent electron acceptors, as evidenced by reports of air-stable radical forms of large aromatic diimides such as naphthalene and perylene diimides. These ions have also been observed to exhibit anion-π interaction tendencies of interest in molecular recognition applications. The benefits of phosphonium incorporation, however, have not yet been extended to the smallest benzene diimides. Here, we report that dibrominated pyromellitic diimide and mellophanic diimide both readily undergo substitution reactions with phosphine sources to yield bisphosphonium compounds. In the single crystalline form, these dications display anion-π interactions and, in the case of mellophanic diimide, the stabilization of a bromide-water H-bonding ring pattern. The reaction of these dications with chemical reductants readily provides the singly and doubly reduced redox states, which were characterized by UV-vis spectroscopy and found to exhibit intense absorptions extending into the near-IR region. Taken together, this work demonstrates that phosphonium incorporation onto congested aromatic diimide scaffolds is synthetically viable and produces unusual electron-poor compounds.

Methane emission is independent from silicon availability in warm-temperate Chamaecyparis obtusa forest soils from diverse topographic positions

It has been recently reported that silicon (Si) increases methane (CH4) emission from peats through mobilizing phosphorus and organic carbon bound to iron minerals and stimulating microbial activities. However, it is unknown whether this effect of Si applies in other environments, such as warm temperate forest soils that function primarily as a CH4 sink but occasionally as a CH4 source. We tested our hypothesis that CH4 emission should increase with Si availability in warm temperate forest soils under anaerobic conditions, by incubating four soil samples collected from a variety of topographic positions in the Kiryu Experimental Watershed, in Shiga, Japan. The soil characteristics including soil pH and total phosphorus and iron contents varied among the soils. Much greater CH4 emission was observed in the soils from the riparian wetland areas than in those from the upland areas. The onset of methanogenesis was not accelerated by Si addition during the incubation. At the end of the incubation, the Si addition did not increase total CH4 production from the soils. A lack of the Si effects would be due to low quantities of phosphorus retained by iron minerals in the entire area of this watershed and high abundance of more potent electron acceptors in the upland. Overall, our results suggest that increasing Si availability exerts little influence on CH4 emissions from warm temperate forest soils under the used experimental conditions in this watershed.

Facile fabrication of fluorescent Fe-doped carbon quantum dots for dopamine sensing and bioimaging application.

In this paper, we have presented a novel strategy to fabricate Fe-doped carbon quantum dots (Fe-CQDs) for dopamine sensing applications. The Fe-CQDs are obtained by one step hydrothermal carbonization, using ethylenediamine tetraacetic acid salts and ferric nitrate as the carbon and iron source, which simultaneously incorporates Fe (dopamine-bonding site) and luminescent carbon quantum dots (fluorophores). The added dopamine containing catechol groups might form complexes with Fe ions (doped in CQDs) due to coordination. Subsequently, dopamine was oxidized to generate dopamine-quinone (a known potent electron acceptor) species by ambient O2. Thus, the coordination induced dopamine in proximity to the CQDs, which provided favourable electron acceptors in close proximity to the CQDs and produced high quenching efficiencies. Such fluorescence responses can be used for well quantifying dopamine in the range of 0.01-50 μM with a detection limit of 5 nM (S/N = 3). The proposed sensing system has been successfully used for the assay of dopamine in human urine samples. Preliminary cell image study indicates that the obtained Fe-CQDs possess high photostability and low cytotoxicity, which make them promising for biological applications.

Exploring microbial N2 O reduction: a continuous enrichment in nitrogen free medium.

N2 O is a potent greenhouse gas, but also a potent electron acceptor. In search of thermodynamically favourable - yet undescribed - metabolic pathways involving N2 O reduction, we set up a continuous microbial enrichment, inoculated with activated sludge, fed with N2 O as the sole electron acceptor and acetate as an electron donor. A nitrogen-free mineral medium was used with the intention of creating a selective pressure towards organisms that would use N2 O directly as source of nitrogen for cell synthesis. Instead, we obtained a culture dominated by microorganisms of the Rhodocyclaceae family growing by N2 O reduction to N2 coupled to N2 fixation. Biomass yields of this culture were 40% lower than those of a previously reported culture grown under comparable conditions but with an NH4+-amended medium, as expected from the extra energy expense of N2 fixation. Interestingly, we found no significant difference in yields whether N2 O or acetate was the growth-limiting substrate in the chemostat in contrast to the study with NH4+-amended medium, in which biomass yields were roughly 30% lower during acetate limiting conditions.

Low Bandgap Conjugated Polymers Based on a Nature-Inspired Bay-Annulated Indigo (BAI) Acceptor as Stable Electrochromic Materials

The donor–acceptor (D–A) approach, which is to incorporate alternating electron-rich (donor) and electron-deficient (acceptor) units along the conjugated polymer mainchain, has become an effective method to provide an informed search for high performance electrochromic low bandgap polymers. Herein a potent electron acceptor, namely, a much more soluble version of the nature-inspired bay-annulated indigo (BAI), was employed in the synthesis of two solution-processable donor–acceptor polymers for efficient electrochromic devices (ECDs). The devices fabricated from spin-coated polymer thin films can switch reversibly between deep blue and transmissive light green hues, with high optical contrasts in the visible and near-infrared (NIR) regions, good coloration efficiency and promising ambient stability. In particular, electrochromic devices based on the copolymer containing a carbazole donor unit exhibit optical contrasts of 41% and 59% in the visible and NIR regions, respectively, and a long-term stability o...

Shallow breathing: bacterial life at low O2

Competition for molecular oxygen (O(2)) among respiratory microorganisms is intense because O(2) is a potent electron acceptor. This competition leads to the formation of microoxic environments wherever microorganisms congregate in aquatic, terrestrial and host-associated communities. Bacteria can harvest O(2) present at low, even nanomolar, concentrations using high-affinity terminal oxidases. Here, we report the results of surveys searching for high-affinity terminal oxidase genes in sequenced bacterial genomes and shotgun metagenomes. The results indicate that bacteria with the potential to respire under microoxic conditions are phylogenetically diverse and intriguingly widespread in nature. We explore the implications of these findings by highlighting the importance of microaerobic metabolism in host-associated bacteria related to health and disease.

Donor-Substituted Octacyano[4]dendralenes: Investigation of π-Electron Delocalization in Their Radical Ions

Symmetrically and unsymmetrically electron-donor-substituted octacyano[4]dendralenes were synthesized and their opto-electronic properties investigated by UV/vis spectroscopy, electrochemical measurements (cyclic voltammetry (CV) and rotating disk voltammetry (RDV)), and electron paramagnetic resonance (EPR) spectroscopy. These nonplanar push-pull chromophores are potent electron acceptors, featuring potentials for first reversible electron uptake around at -0.1 V (vs Fc(+)/Fc, in CH2Cl2 + 0.1 M n-Bu4NPF6) and, in one case, a remarkably small HOMO-LUMO gap (ΔE = 0.68 V). EPR measurements gave well-resolved spectra after one-electron reduction of the octacyano[4]dendralenes, whereas the one-electron oxidized species could not be detected in all cases. Investigations of the radical anions of related donor-substituted 1,1,4,4-tetracyanobuta-1,3-diene derivatives revealed electron localization at one 1,1-dicyanovinyl (DCV) moiety, in contrast to predictions by density functional theory (DFT) calculations. The particular factors leading to the charge distribution in the electron-accepting domains of the tetracyano and octacyano chromophores are discussed.

Non‐Volatile Photochemical Gating of an Epitaxial Graphene/Polymer Heterostructure

Electronic devices using epitaxial graphene on Silicon Carbide require encapsulation to avoid uncontrolled doping by impurities deposited in ambient conditions. Additionally, interaction of the graphene monolayer with the substrate causes relatively high level of electron doping in this material, which is rather difficult to change by electrostatic gating alone. Here we describe one solution to these problems, allowing both encapsulation and control of the carrier concentration in a wide range. We describe a novel heterostructure based on epitaxial graphene grown on silicon carbide combined with two polymers: a neutral spacer and a photoactive layer that provides potent electron acceptors under UV light exposure. Unexposed, the same double layer of polymers works well as capping material, improving the temporal stability and uniformity of the doping level of the sample. By UV exposure of this heterostructure we controlled electrical parameters of graphene in a non-invasive, non-volatile, and reversible way, changing the carrier concentration by a factor of 50. The electronic properties of the exposed SiC/ graphene/polymer heterostructures remained stable over many days at room temperature, but heating the polymers above the glass transition reversed the effect of light. The newly developed photochemical gating has already helped us to improve the robustness (large range of quantizing magnetic field, substantially higher opera- tion temperature and significantly enhanced signal-to-noise ratio due to significantly increased breakdown current) of a graphene resistance standard to such a level that it starts to compete favorably with mature semiconductor heterostructure standards. [2,3]

All‐Carbon Scaffolds by Rational Design

The search for new molecular and regular polymeric allotropes of carbon has greatly stimulated the preparation and investigation of pi-conjugated acetylenic macrocycles, which often represent substructures of proposed 2D carbon networks. Perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with large, multi-nanometer-sized all-carbon cores are potent electron acceptors, and their optoelectronic as well as stability and solubility properties are greatly enhanced by peripheral donor substitution. Acetylenic scaffolding into three dimensions has generated an expanded cubane with a C(56) core, the first representative of a new class of "platonic" objects. Exceptional chiroptical properties displayed by enantiomerically pure alleno-acetylenic, shape-persistent macrocycles promise fascinating perspectives for the development of molecular and supramolecular chiroptical materials.

Electrocatalytic CO 2 Conversion to Oxalate by a Copper Complex

Global warming concern has dramatically increased interest in using CO2 as a feedstock for preparation of value-added compounds, thereby helping to reduce its atmospheric concentration. Here, we describe a dinuclear copper(I) complex that is oxidized in air by CO2 rather than O2; the product is a tetranuclear copper(II) complex containing two bridging CO2-derived oxalate groups. Treatment of the copper(II) oxalate complex in acetonitrile with a soluble lithium salt results in quantitative precipitation of lithium oxalate. The copper(II) complex can then be nearly quantitatively electrochemically reduced at a relatively accessible potential, regenerating the initial dinuclear copper(I) compound. Preliminary results demonstrate six turnovers (producing 12 equivalents of oxalate) during 7 hours of catalysis at an applied potential of -0.03 volts versus the normal hydrogen electrode.

Acetylene-Derived Strong Organic Acceptors for Planar and Nonplanar Push−Pull Chromophores

Though investigated for decades, interest in push-pull chromophores (D-pi-A), strong electron donors (D) connected by pi-conjugating spacers to strong electron acceptors (A), continues to grow. Such chromophores are of substantial interest for optoelectronic devices such as waveguides. Also, strong donors and acceptors form bimolecular charge-transfer (CT) complexes and salts, some of which exhibit electrical conductivity and magnetic behavior. Furthermore, strong organic acceptors are increasingly explored as dopants in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. This Account describes systematic efforts pursued over the past decade in our laboratory to generate new families of organic electron acceptors (A) and conjugate them via pi-spacers to electron donors (D) under formation of push-pull systems with intense intramolecular CT interactions and high third-order optical nonlinearities. First, we describe donor-acceptor-substituted tetraethynylethenes (TEEs). In these chromophores, the peripherally attached p-nitrophenyl acceptors and N,N-dimethylanilino donors behave as nearly independent redox centers. Acetylenic scaffolding using TEE building blocks produces large all-carbon sheets, such as perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with potent electron-acceptor properties. Arylated TEEs act as molecular switches allowing two-way photochemical interconversion that is not perturbed by thermal isomerization pathways. Upon sequential substitution of the acetylene moieties in TEEs, we formed another family of potent acceptors, the cyanoethynylethenes (CEEs). Donor-substituted CEEs are planar CT chromophores with very high third-order optical nonlinearities. Their high environmental stability allows for the formation of thin films by vapor-phase deposition. Through careful analysis of the physicochemical properties of CEEs, we established useful guidelines for evaluating and tuning the optical gap in strong push-pull chromophores: increasing the length of the pi-spacer in D-pi-A systems reduces ground-state D-A conjugation and lowers the HOMO-LUMO gap. By taking advantage of "click-chemistry"-type [2 + 2] cycloadditions of tetracyanoethene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) with appropriately activated alkynes, followed by retro-electrocyclization, the formation of donor-substituted 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs), 1,1,2,4,4-pentacyanobuta-1,3-dienes (PCBDs), and novel TCNQ adducts is possible. Some of these stable, nonplanar CT chromophores form high optical quality amorphous thin films by vapor-phase deposition. Despite donor substitution, the new acceptors (TCBDs, PCBDs, and the TCNQ adducts) rival TCNE and TCNQ in their ease for reversible electron uptake. High-yielding cycloaddition/retro-electrocyclization cascades provide access to multivalent, dendritic chromophores acting as "molecular batteries" with a remarkable capacity for multiple electron uptake in a narrow potential range. Finally, we used a one-pot protocol for electronically controlled consecutive TCNE and tetrathiafulvalene (TTF) additions to end-capped polyynes to form [AB]-type oligomers with a dendralene-type backbone.

Inhibition of endothelial nitric oxide synthase activity and suppression of endothelium-dependent vasorelaxation by 1,2-naphthoquinone, a component of diesel exhaust particles

Diesel exhaust particles contain redox-active quinones, such as 9,10-phenanthraquinone (9,10-PQ) and 1,2-naphthoquinone (1,2-NQ), which act as potent electron acceptors, thereby altering electron transfer tgljoint @/Set Line Joint Styleon proteins. We have previously found that 9,10-PQ inhibits constitutive nitric oxide synthase (NOS) activity, by shunting electrons away from NADPH on the cytochrome P450 reductase domain of NOS, and thus suppresses acetylcholine (Ach)-induced vasorelaxation in the aortic ring. However, the effect of 1,2-NQ on endothelial NOS (eNOS) activity is still poorly understood. With the membrane fraction of cultured bovine aortic endothelial cells, we found that 1,2-NQ was a potent inhibitor of eNOS with an IC50 value of 1.4 microM, whereas trans-1,2-dihydroxy-1,2-dihydronaphthalene (1,2-DDN), a redox-negative naphthalene analog of 1,2-NQ, did not show such an inhibitory action. Although 1,2-DDN (5 microM) did not affect Ach-mediated vasorelaxation, 1,2-NQ caused a significant suppression of Ach-induced endothelium-dependent vasorelaxation in the aortic ring. However, 1,2-NQ did not affect sodium nitroprusside-induced endothelium-independent vasorelaxation. These results suggest that 1,2-NQ is an environmental quinone that inhibits eNOS activity, thereby disrupting NO-dependent vascular tone.

ChemInform Abstract: Synthesis and Novel Reactivity of Halomethyldimethylsulfonium Salts.

Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b−d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (SN2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.

Synthesis and novel reactivity of halomethyldimethylsulfonium salts

Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (S(N)2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.

Synthesis, electrochemistry and ab initio molecular orbital calculations on some norbornane- and bicyclo[2.2.2]octane-fused 5,12-bis(dicyanomethylidene)naphthalene systems

A series of norbornane- and bicyclo[2.2.2]octane-fused tetracyanonaphthoquinodimethane (benzoTCNQ) derivatives, 4,6,8,10 and 12 has been synthesized. Cyclic voltammetry measurements revealed two one-electron reduction waves for the benzo-TCNQ systems 4, 8 and 10 which possess either a cyclobutane or a norbornane moiety fused to the quinonoid ring, but a single (presumably two-electron) reduction wave for 6 and 12 which possess a bicyclo[2.2.2]octane group fused to the gmnonoid ring. The benzo-TCNQ systems were found to be potent electron acceptors. The results of (U)HF/3-21G calculations carried out on representative benzo-TCNQ derivatives suggest that steric interactions between the quinonoid ring and its adjacent fused alicyclic group are largely responsible for the observed decrease in the electron affinities along the series: 8 > 4 > 6. The MO calculations further suggest that LUMO energies of neutral TCNQ derivatives are qualitatively reliable predictors of electron affinities. The calculated (gas phase) internal reorganization energies, λi, for the benzo-TCNQ systems are ca. 54 kJ mol–1 and are comparable to that calculated for the dicyanovinyl (DCV) system, 27. The similarity between the λi values for the benzo-TCNQ systems and 27, together with the experimental finding that benzo-TCNQ systems are reduced at ca. 1.7 V less negative potentials than 27, should make the norbornane- and bicyclo [2.2.2] octane-benzo-TCNQ systems superior to the DCV moiety as acceptor chromophores in giant multichromophoric systems.

The human dioxin‐inducible NAD(P)H:quinone oxidoreductase cDNA‐encoded protein expressed in COS‐1 cells is identical to diaphorase 4

NAD(P)H: quinone oxidoreductase (NQO1) is believed to be protective against cancer and toxicity caused by exposure to quinones and their metabolic precursors. This enzyme catalyzes the two-electron reduction of compounds, compared with one-electron reduction mediated by NADPH: cytochrome-P450 oxidoreductase which produces toxic and mutagenic free radicals. Recently we cloned and sequenced the cDNA encoding human 2.3,7,8-tetrachlorodibenzo-p-dioxin (dioxin)-inducible cytosolic NQO1 [Jaiswal et al. (1988) J. Biol. Chem. 263, 13572-13578] and provided preliminary evidence that this enzyme may correspond to diaphorase 4, an enzymatic activity present in various tissues that catalyzes the reduction of a variety of quinones by both NADH and NADPH [Edwards et al. (1980) Biochem. J. 187, 429-436]. In the present report we characterize the catalytic properties of the protein encoded by the NQO1 cDNA. The enzyme was synthesized in monkey kidney COS-1 cells transfected with a pMT2-based expression plasmid containing the NQO1 cDNA. Western blot analysis of the transfected cells using an antibody against rat liver cytosolic NQO1 revealed a 31-kDa band that was not detected in nontransfected cells. This band corresponded to a polypeptide with the same electrophoretic mobility as the endogenous NQO1 protein detected in the human hepatoblastoma (Hep-G2) cells with the same antibody. The immunoreactive protein detected in human Hep-G2 cells was induced approximately fourfold by exposure of the cultures to dioxin, an increase commensurate with the increased in quinone oxidoreductase activity. These studies suggest that the protein encoded by NQO1 cDNA is indeed similar, if not identical, to the dioxin-inducible protein band detected in human Hep-G2 cells. Further characterization of the product of NQO1 cDNA, which was present at approximately 20-30-fold higher levels in transfected COS cells than the endogenous product in uninduced human Hep-G2 cells indicated that it had very high capacity (greater than 1000-fold over background) to catalyze the reduction of 2.6-dichloroindophenol and menadione. Besides these two commonly used substrates for quinone reductase, the expressed NQO1 protein also effectively metabolized 2,6-dimethylbenzoquinone, methylene blue, p-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-benzoquinone, with the latter being the most potent electron acceptor at 50 microM concentration of the substrate.

Mechanism of inhibition of reverse transcriptase by quinone antibiotics. II. Dependence on putative quinone pocket on the enzyme molecule.

Inhibition of avian myeloblastosis virus (AMV) reverse transcriptase by natural and synthetic quinones including antibiotics could be accounted for by an oxidation-reduction reaction. The quinones were shown to function as electron acceptors as revealed by the catalytic oxidation of NADH by Clostridium kluyveri diaphorase which was in excellent agreement with enzyme inhibition activity. The kinetics of inhibition of AMV reverse transcriptase by three synthetic quinones with different core structures, i.e., 6-methoxy-5,8-dihydroquinoline-5,8- dione, 5,8-dihydroisoquinoline-5,8-dione and 1,4-naphthoquinone, were studied. These quinones inhibited reverse transcriptase in the same manner as streptonigrin (STN) and were shown to act at a single class of reaction site(s) on the enzyme molecule. In contrast, the quinones with bulky substituents, i.e., 7-(2-nitrophenethylamino)-5,8-dihydroisoquinoline-5,8-dione and 7-methoxy-6-methyl-3-piperidino-5,8-dihydroisoquinoline-5,8-dione, were inactive as inhibitors of reverse transcriptase, whereas they retained competent catalytic activities in the oxidation of NADH by C. kluyveri diaphorase. Based on these observations, the existence of a specific site of interaction on the enzyme molecule, referred to as a quinone pocket, was proposed. The quinone pocket might play a crucial role in the early sequence of events leading to the inhibition of reverse transcriptase by quinones including STN and sakyomicin A (SKM). Access of SKM to a quinone pocket might be restricted due to its bulky structure in the vicinity of the quinone group. This is inferred from unsuccessful inhibition of reverse transcriptase by the quinones with bulky substituents, resulting in much poorer inhibition of reverse transcriptase in spite of more potent electron acceptor activity in the oxidation-reduction system as compared with those of STN.

Mechanism of inhibition of reverse transcriptase by quinone antibiotics.

Inhibition of avian myeloblastosis virus (AMV) reverse transcriptase by natural and synthetic quinones including antibiotics could be accounted for by an oxidation-reduction reaction. The quinones were shown to function as electron acceptors as revealed by the catalytic oxidation of NADH by Clostridium kluyveri diaphorase which was in excellent agreement with enzyme inhibition activity. The kinetics of inhibition of AMV reverse transcriptase by three synthetic quinones with different core structures, i.e., 6-methoxy-5, 8-dihydroquinoline-5, 8-dione, 5, 8-dihydroisoquinoline-5, 8-dione and 1, 4-naphthoqumone, were studied. These quinones inhibited reverse transcriptase in the same manner as streptonigrin (STN) and were shown to act at a single class of reaction site(s) on the enzyme molecule. In contrast, the quinones with bulky substituents, i.e., 7-(2-nitrophenethylamino)-5, 8-dihydroisoquinoline-5, 8-dione and 7-methoxy6-methyl-3-piperidino-5, 8-dihydroisoquinoline-5, 8-dione, were inactive as inhibitors of reverse transcriptase, whereas they retained competent catalytic activities in the oxidation of NADH by C. kluyveri diaphorase. Based on these observations, the existence of a specific site of interaction on the enzyme molecule, referred to as a quinone pocket, was proposed. The quinone pocket might play a crucial role in the early sequence of events leading to the inhibition of reverse transcriptase by quinones including STN and sakyomicin A (SKM). Access of SKM to a quinone pocket might be restricted due to its bulky structure in the vicinity of the quinone group. This is inferred from unsuccessful inhibition of reverse transcriptase by the quinones with bulky substituents, resulting in much poorer inhibition of reverse transcriptase in spite of more potent electron acceptor activity in the oxidationreduction system as compared with those of STN.

Ionicity and paramagnetism of strong organic charge-transfer complexes

Ionic charge-transfer (CT) complexes were prepared by mixing neutral solutions of the potent electron acceptor TCNQF4 (7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane) with the strong donors M2P(5,10-dihydro-5,10-diemethylphenazine) and TMPD(N,N,N′,N′-tetramethyl-p-phenylenediamine). M2P–TCNQF4 [complex (1)] and TMPD–TCNQF4 [complex (2)] were obtained as deep blue solids, the latter only in polycrystalline form. Complex (1) crystallizes in the triclinic space group P1̄ with a = 7.002 (2), b = 8.787(2), c = 9.551(3), α = 108.53(2), β = 99.68(2), γ = 91.88(2), and Z = 1. The planar M2P+⋅ and TCNQF−4⋅ radical ions form mixed regular stacks. The structure refinement gave R = 0.039 and Rw = 0.033 for 1044 counter data. The ionicity γ and structure of mixed ⋅⋅⋅D+γA−γD+γA−γ⋅⋅⋅ stacks are closely related to the paramagnetic susceptibility χ(T). The two TCNQF4 complexes are shown to be the first highly ionic (γ≳0.9) systems. χ(T) for complex (1) follows a Heisenberg antiferromagnetic chain with J = 175 cm−1 for T≳122 K, below which χ(T) decreases steeply as expected for a dimerization transition. χ(T) for complex (2) can be fit to a power law T−α, with α = 0.75±0.10, and also indicates γ≳0.9. Both complexes (1) and (2) are on the paramagnetic side of the paramagnetic–diamagnetic interface, while the finite activation energy for paramagnetism in the less ionic M2P–TCNQ and TMPD–TCNQ complexes puts them on the diamagnetic side. The elementary excitations of these related CT complexes with different ionicities are modeled.