Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(II) derivative anchored with a 'scorpionate' precursor as a potential electrocatalyst for heterogeneous H2 evolution.

A new doubly carboxylato-bridged Co(II) dinuclear complex, [Co(bdtbpza)(NCS)]2 (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(II) is penta-coordinated, leading to a distorted trigonal-bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(II) ions in 1 was found based on the isotropic spin Hamiltonian H = -J(S1·S2) for the Si = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.

2,5-Thienylene-Strapped [26]Hexaphyrin as Multifunctional Chemosensor for Hg2+, Cu2+, and F- Ions.

The sensing behavior of 2,5-thienylene-bridged tetrakis(2,6-dichlorophenyl)-[26]hexaphyrin (2) towards various metal ions and anions were investigated by UV-vis and fluorescence spectroscopies. Using this strapped hexaphyrin (2), the molecular sensor displayed highly selective and sensitive colorimetric responses to Cu2+ and Hg2+ in MeOH/THF. The spectral changes are distinctive enough in the visible region of the spectrum to enable naked-eye detection. The detection limits of Cu2+ and Hg2+ using this chemo-sensor in a mixed MeOH/THF solution were 1.978 and 1.283 µM, respectively, and 1.052 µM for F- in dichloromethane. Chemosensor 2,5-thienylene strapped [26]hexaphyrin (2) shows absorption responses both a 1 : 1 molecular ratio for 2 interacting with Cu2+ and Hg2+ and a 1 : 2 ratio between 2 and F- ions.

Overcoming small-bandgap charge recombination in visible and NIR-light-driven hydrogen evolution by engineering the polymer photocatalyst structure.

Designing an organic polymer photocatalyst for efficient hydrogen evolution with visible and near-infrared (NIR) light activity is still a major challenge. Unlike the common behavior of gradually increasing the charge recombination while shrinking the bandgap, we present here a series of polymer nanoparticles (Pdots) based on ITIC and BTIC units with different π-linkers between the acceptor-donor-acceptor (A-D-A) repeated moieties of the polymer. These polymers act as an efficient single polymer photocatalyst for H2 evolution under both visible and NIR light, without combining or hybridizing with other materials. Importantly, the difluorothiophene (ThF) π-linker facilitates the charge transfer between acceptors of different repeated moieties (A-D-A-(π-Linker)-A-D-A), leading to the enhancement of charge separation between D and A. As a result, the PITIC-ThF Pdots exhibit superior hydrogen evolution rates of 279 µmol/h and 20.5 µmol/h with visible (>420 nm) and NIR (>780 nm) light irradiation, respectively. Furthermore, PITIC-ThF Pdots exhibit a promising apparent quantum yield (AQY) at 700 nm (4.76%).

Electronic Structure Optimization of PdZn-Graphitic Carbon Nitride Nanocomposites as Electrocatalysts for Selective CO2 to CO Conversion.

Herein, a novel PdZn/g-C3N4 nanocomposite electrocatalyst, PdZnGCN, prepared from a facile hydrothermal reduction procedure for an efficient CO2 to CO conversion has been examined. This composite catalyst reduces CO2 at a thermodynamic overpotential of 0.79 V versus RHE with a 93.6% CO Faradaic efficiency and a CO partial current density of 4.4 mA cm-2. Moreover, the turnover frequency for PdZnGCN reaches 20 974 h-1 with an average selectivity of 95.4% for CO after 1 h and an energy efficiency approaching 59%, which is superior to most reported noble metals and metal alloys as electrocatalysts. The enhanced catalytic activity of this nanocomposite is due to synergistic interactions between PdZn and g-C3N4 as evidenced by optimum work function, zeta potential, CO desorption rate, and downshifted d-band center. Furthermore, suppressed grain growth during the formation of nanocomposites also results in faster reaction kinetics, as demonstrated by a lower Tafel slope (93.6 mV/dec) and a larger electrochemically active surface, consequently enhancing the overall performance.

Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics.

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH2 ) and electron-withdrawing (R=NO2 ) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L1 )(L2 )]n (1) and [Zn(L1 )(L3 )]n (2) [L1 =2-(2-pyridyl) benzimidazole (Pbim), L2 =5-aminoisophthalate (Aip), and L3 =5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2 . Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.

Thin Film Growth of 3D Sr-based Metal-Organic Framework on Conductive Glass via Electrochemical Deposition.

Integration of metal-organic frameworks (MOFs) as components of advanced electronic devices is at a very early phase of development and the fundamental issues related to their crystal growth on conductive substrate need to be addressed. Herein, we report on the structural characterization of a newly synthesized Sr-based MOF {[Sr(2,5-Pzdc)(H2 O)2 ] ⋅ 3 H2 O}n (1) and the uniform crystal growth of compound 1 on a conducting glass (fluorine doped tin oxide (FTO)) substrate using electrochemical deposition techniques. The Sr-based MOF 1 was synthesized by the reaction of Sr(NO3 )2 with 2,5-pyrazinedicarboxylic acid dihydrate (2,5-Pzdc) under solvothermal conditions. A single-crystal X-ray diffraction analysis revealed that 1 has a 3D structure and crystallizes in the triclinic P 1 ‾ space group. In addition, the uniform crystal growth of this MOF on a conducting glass (FTO) substrate was successfully achieved using electrochemical deposition techniques. Only a handful of MOFs have been reposed to grown on conductive surfaces, which makes this study an important focal point for future research on the applications of MOF-based devices in microelectronics.

Intrinsic Ultralow-Threshold Laser Action from Rationally Molecular Design of Metal-Organic Framework Materials.

Metal-organic frameworks (MOFs) are superior for multiple applications including drug delivery, sensing, and gas storage because of their tunable physiochemical properties and fascinating architectures. Optoelectronic application of MOFs is difficult because of their porous geometry and conductivity issues. Recently, a few optoelectronic devices have been fabricated by a suitable design of integrating MOFs with other materials. However, demonstration of laser action arising from MOFs as intrinsic gain media still remains challenging, even though some studies endeavor on encapsulating luminescence organic laser dyes into the porous skeleton of MOFs to achieve laser action. Unfortunately, the aggregation of such unstable laser dyes causes photoluminescence quenching and energy loss, which limits their practical application. In this research, unprecedently, we demonstrated ultralow-threshold (∼13 nJ/cm2) MOF laser action by a judicious choice of metal nodes and organic linkers during synthesis of MOFs. Importantly, we also demonstrated that the white random lasing from the beautiful microflowers of organic linkers possesses a porous network, which is utilized to synthesize the MOFs. The highly luminescent broad-band organic linker 1,4-NDC, which itself exhibits a strong white random laser, is used not only to achieve the stimulated emission in MOFs but also to reduce the lasing threshold. Such white lasing has multiple applications from bioimaging to the recently developed versatile Li-Fi technology. In addition, we showed that the smooth facets of MOF microcrystals can show Fabry-Perot resonant cavities having a high quality factor of ∼103 with excellent photostability. Our unique discovery of stable, nontoxic, high-performance MOF laser action will open up a new route for the development of new optoelectronic devices.

Hydrogel-based zinc ion sensor on optical fiber with high resolution and application to neural cells.

Solid-state zinc ion sensor is developed with high enough resolution and reproducibility for the potential application in brain injury monitoring. An optical diffuser is incorporated into the zinc ion sensor based on optical fiber and hydrogel doped with the fluorescent zinc ion probe molecule meso-2,6-Dichlorophenyltripyrrinone (TPN-Cl2). The diffuser transforms the high-peak-intensity excitation light near the fiber end into a broad light with moderate local intensity to reduce the degradation of the probe molecule. Reversible detection can be reached for 1, 2, and 5 µM (10-6 Molar), with slopes 0.3, 0.6, and 0.8 respectively. This is the pathophysiological concentration range after brain injury. The sensor is applied to neuron-glial cultures and macrophage under the stimulation of lipopolysaccharide (LPS), KCl and oxygen/glucose deprivation (OGD) that reflect inflammation, depolarization and ischemia respectively, mimicking events after brain injury. The zinc ion level is raised to 4-5 µM after LPS treatment, and then reduced to <3 µM after the co-treatment with the herbal drug silymarin. The results suggest the conditions of the neural cells under stress can be monitored.

Development of Hybrid Pseudohalide Tin Perovskites for Highly Stable Carbon-Electrode Solar Cells.

Tin-based perovskites degrade rapidly upon interaction with water and oxygen in air because Sn-I bonds are weak. To address this issue, we developed novel tin perovskites, FASnI(3-x)(SCN)x (x = 0, 1, 2, or 3), by employing a pseudohalide, thiocyanate (SCN-), as a replacement for halides and as an inhibitor to suppress the Sn2+/Sn4+ oxidation. The structural and electronic properties of pseudohalide tin perovskites in this series were explored with quantum-chemical calculations by employing the plane-wave density functional theory (DFT) method; the corresponding results are consistent with the experimental results. Carbon-based perovskite devices fabricated with tin perovskite FASnI(SCN)2 showed about a threefold enhancement of the device efficiency (2.4%) relative to that of the best FASnI3-based device (0.9%), which we attribute to the improved suppression of the formation of Sn4+, retarded charge recombination, enhanced hydrophobicity, and stronger interactions between Sn and thiocyanate for FASnI(SCN)2 than those for FASnI3. After the incorporation of phenylethyleneammonium iodide (PEAI, 10%) and ethylenediammonium diiodide (EDAI2, 5%) as coadditives, the FASnI(SCN)2 device gave the best photovoltaic performance with JSC = 20.17 mA cm-2, VOC = 322 mV, fill factor (FF) = 0.574, and overall efficiency of power conversion PCE = 3.7%. Moreover, these pseudohalide-containing devices display negligible photocurrent-voltage hysteresis and great stability in ambient air conditions.

Development of Novel Mixed Halide/Superhalide Tin-Based Perovskites for Mesoscopic Carbon-Based Solar Cells.

Tin perovskites suffer from poor stability and a self-doping effect. To solve this problem, we synthesized novel tin perovskites based on superhalide with varied ratios of tetrafluoroborate to iodide and implemented them into solar cells based on a mesoscopic carbon-electrode architecture because film formation was an issue in applying this material for a planar heterojunction device structure. We undertook quantum-chemical calculations based on plane-wave density functional theory (DFT) methods and explored the structural and electronic properties of tin perovskites FASnI3-x(BF4)x in the series x = 0, 1, 2, and 3. We found that only the x = 2 case, FASnI(BF4)2, was successfully produced, beyond the standard FASnI3. The electrochemical impedance and X-ray photoelectron spectra indicate that the addition of tin tetrafluoroborate instead of SnI2 suppressed trap-assisted recombination by decreasing the Sn4+ content. The power conversion efficiency of the FASnI(BF4)2 device with FAI and Sn(BF4)2 in an equimolar ratio improved 72% relative to that of a standard FASnI3 solar cell, with satisfactory photostability under ambient air conditions.

Zn(II) and Co(II) derivatives anchored with scorpionate precursor: Antiproliferative evaluation in human cancer cell lines.

A 'scorpionate' type precursor [bdtbpza = bis(3,5-di-t-butylpyrazol-1-yl)acetate] has been employed to synthesize two mononuclear ZnII and CoII derivatives, namely [Zn(bdtbpza)2 (H2O)2]·2.5CH3OH·2[(CH3)3C-C3H2N2-C(CH3)3] (1) and [Co(bdtbpza)2(CH3OH)4] (2) in good yield. Single crystal X-ray diffraction analysis reveals that in 1, the ZnII atom is tetrahedrally surrounded by a pair of Oacetate atoms of two bis(pyrazol-1-yl)acetate units and two water molecules; while in 2, the CoII atom shows an octahedral environment coordinating a pair of Oacetate atoms of two bis(pyrazol-1-yl)acetate units along with four methanol molecules. The EPR spectra of 2 recorded at 77 and 298 K confirmed the tetragonal symmetry of the high spin Co(II). The DFT (Density functional theory) computation is in good agreement with the geometry proposed for compounds 1 and 2. Both the compounds display a high antiproliferative activity against HCT116 (colorectal carcinoma) and A2780 (ovarian carcinoma) cell lines compared to human normal dermal fibroblasts. In the case of A2780 cells, compounds 1 and 2 exhibit IC50 values that are similar to those described for cisplatin, a widely used chemotherapeutic drug. Exposure of A2780 cells to the IC50 concentration of each compound led to an increase of the number of apoptotic and autophagic cells. In the case of compound 1, the accumulation of intracellular ROS (Reactive oxygen species) is responsible for triggering A2780 cell death.

Ni and Pd N-confused porphyrin complexes as catalysts for the synthesis of cyclic carbonates from epoxides and CO2.

We have demonstrated the design of a novel bifunctional catalyst that is based on an N-confused tetraphenylporphyrin (NCTPP) motif for the cycloaddition of an epoxide to carbon dioxide via cooperative activation of the epoxide through a Pd(ii) or Ni(ii) metal center and a peripheral benzoate moiety with percent conversions of up to 99% and TON = 7000.

2,5-Thienylene-Strapped Bicyclic and Tricyclic Expanded Porphyrins.

An [18]thiaporphyrin[36]dithiaoctaphyrin-[18]thiaporphyrin tricyclic macrocycle, fused through the 2,5-thienylene bridging moiety, was isolated during the preparation of 2,5-thienylene-strapped [26]hexaphyrin containing o-dichlorophenyl groups as meso substituents. The spectroscopic data of the 2,5-thienylene-strapped [26]hexaphyrin verified contributions of aromaticity from ring currents of both the [18]thiaporphyrin and the [26]hexaphyrin. The crystal structure of the tricyclic macrocycle revealed a distorted [36]dithiaoctaphyrin central core with two [18]thiaporphyrin sidewheels oriented nearly perpendicular to the mean-plane of dithiaoctaphyrin, implying the existence of independent π-conjugated systems. Both the absorption maximum at 441 nm and the chemical shifts in the 1 H NMR spectrum of the tricyclic macrocycle are dominated by diatropic ring currents of two aromatic [18]thiaporphyrin sidewheels.

Bioinorganic Chemistry of the Natural [Fe(NO)2] Motif: Evolution of a Functional Model for NO-Related Biomedical Application and Revolutionary Development of a Translational Model.

Identification of the distinctive electron paramagnetic resonance signal at g = 2.03 in the yeast cells and liver of mice treated with carcinogens opened the discovery and investigation of the natural [Fe(NO)2] motif in the form of dinitrosyliron complexes (DNICs). In this Viewpoint, a chronological collection of the benchmark for the study of DNIC demonstrates that the preceding study of its biological synthesis, storage, transport, transformation, and function related to NO physiology inspires the biomimetic study of structural and functional models supported by thiolate ligands to provide mechanistic insight at a molecular level. During the synthetic, spectroscopic, and theoretical investigations on the structure-to-reactivity relationship within DNICs, control of the Fe-NO bonding interaction and of the delivery of NO+/•NO/HNO/NO- by the supporting ligands and nuclearity evolves into the "redesign of the natural [Fe(NO)2] motif" as a strategy to develop DNICs for NO-related biomedical application and therapeutic approach. The revolutionary transformation of covalent a [Fe(NO)2] motif into a translational model for hydrogenase, triggered by the discovery of redox interconversion among [{Fe(NO)2}9-L•] ↔ {Fe(NO)2}9 ↔ {Fe(NO)2}10 ↔ [{Fe(NO)2}10-L•]-, echoes the preceding research journey on [Fe]/[NiFe]-hydrogenase and completes the development of an electrodeposited-film electrode for electrocatalytic water splitting. Through the 50-year journey, bioinorganic chemistry of DNIC containing the covalent [Fe(NO)2] motif and noninnocent/labile NO ligands highlights itself as a unique metallocofactor to join the longitudinal study between biology/chemistry/biomedical application and the lateral study toward multielectron (photo/electro)catalysis for industrial application. This Viewpoint discloses the potential [Fe(NO)2] motif awaiting continued contribution in order to emerge as a novel application in the next 50 years, whereas the parallel development of bioinorganic chemistry, guided by inspirational Nature, moves the science forward to the next stage in order to benefit the immediate needs for human activity.

A mechanistic study of nitrite reduction on iron(ii) complexes of methylated N-confused porphyrins.

Proton delivery to the prosthetic group is a crucial step to sustain the activity of nitrite reductase. An iron N-confused porphyrin (NCP) complex, which is capable of relaying protons from the outer pyrrolic nitrogen (Nout-H) of the inverted pyrrole ring to the axial coordinated ligand, has been demonstrated to facilitate facile nitrite reduction. Time-dependent FTIR studies on the reaction between [FeII(HCTPPMe)Br] (1) and a nitrite anion revealed a two-step process involving conversion of the starting complex 1 to an {Fe(NO)}7 intermediate, [Fe(CTPPMe)(NO)] (5), before the detection of [Fe(CTPPCH2)(NO)] (3), an {Fe(NO)}6 end product. Moreover, spectroscopic data confirm that Nout-H on the NCP core is indispensable to the proceeding of the nitrite reduction reaction. Mass spectra have detected the coordination of a nitrite to the iron center while DFT theoretical calculations suggest that subsequent intramolecular proton transfer to a nitro group to form [Fe(CTPPMe)(HNO2)] (6a) evokes a homolytic N-OH bond fission on axial nitrous acid due to an enhanced π-back-bonding to produce an {Fe(NO)}7 intermediate and to release a hydroxyl radical. The subsequent oxidation of an {Fe(NO)}7 intermediate by the hydroxyl radical gave the final product, {Fe(NO)}6 [Fe(CTPPCH2)(NO)] (3). This study illustrates a proton assisted small molecule activation on the iron N-confused porphyrin coordination sphere and provides complemental insights into the mechanism of enzymatic nitrite reduction reactions.

Formation of Stable Tin Perovskites Co-crystallized with Three Halides for Carbon-Based Mesoscopic Lead-Free Perovskite Solar Cells.

We synthesized and characterized methylammonium (MA) mixed tri-halide tin perovskites (MASnIBr2-x Clx ) for carbon-based mesoscopic solar cells free of lead and hole-transporting layers. Varied SnCl2 /SnBr2 ratios yielded tin perovskites with three halides (I, Br, and Cl) co-crystallized inside the tin-perovskite. When the SnCl2 proportion was ≥50 % (x≥1), phase separation occurred to give MASnI3-y Bry and MASnCl3-z Brz in the stoichiometric proportions of their precursors, confirmed by XRD. A device with MASnIBr1.8 Cl0.2 (SnCl2 =10 %) showed the best photovoltaic performance: JSC =14.0 mA cm-2 , VOC =380 mV, FF=0.573, and PCE=3.1 %, and long-term stability. Electrochemical impedance spectra (EIS) show superior charge recombination and dielectric relaxation properties for the MASnIBr1.8 Cl0.2 cell. Transient PL decays showed the intrinsic problem of tin-based perovskites with average lifetimes less than 100 ps.

Oxasmaragdyrins as New and Efficient Hole-Transporting Materials for High-Performance Perovskite Solar Cells.

The high performance of the perovskite solar cells (PSCs) cannot be achieved without a layer of efficient hole-transporting materials (HTMs) to retard the charge recombination and transport the photogenerated hole to the counterelectrode. Herein, we report the use of boryl oxasmaragdyrins (SM01, SM09, and SM13), a family of aromatic core-modified expanded porphyrins, as efficient hole-transporting materials (HTMs) for perovskite solar cells (PSCs). These oxasmaragdyrins demonstrated complementary absorption spectra in the low-energy region, good redox reversibility, good thermal stability, suitable energy levels with CH3NH3PbI3 perovskite, and high hole mobility. A remarkable power conversion efficiency of 16.5% (Voc = 1.09 V, Jsc = 20.9 mA cm-2, fill factor (FF) = 72%) is achieved using SM09 on the optimized PSCs device employing a planar structure, which is close to that of the state-of-the-art hole-transporting materials (HTMs), spiro-OMeTAD of 18.2% (Voc = 1.07 V, Jsc = 22.9 mA cm-2, FF = 74%). In contrast, a poor photovoltaic performance of PSCs using SM01 is observed due to the interactions of terminal carboxylic acid functional group with CH3NH3PbI3.

EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor.

A new Cu(II) dinuclear complex, Cu2L2 (1) was afforded employing the potentially pentatentate Schiff base precursor H2L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H2L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H37Ra (ATCC 25177) and M. tuberculosis H37Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL-1. A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.

Iron(iii) bis(pyrazol-1-yl)acetate based decanuclear metallacycles: synthesis, structure, magnetic properties and DFT calculations.

The synthesis, structural aspects, magnetic interpretation and theoretical rationalizations for a new member of the ferric wheel family, a decanuclear iron(iii) complex with the formula [Fe10(bdtbpza)10(µ2-OCH3)20] (1), featuring the N,N,O tridentate bis(3,5-di-tert-butylpyrazol-1-yl)acetate ligand, are reported. The influence of the steric effect on both the core geometry and coordination mode is observed. Temperature dependent (2.0-300 K range) magnetic susceptibility studies carried out on complexes 1 established unequivocally antiferromagnetic (AF) interactions between high-spin iron(iii) centers (S = 5/2), leading to a ground state S = 0. The mechanism of AF intramolecular coupling was proved using a broken-symmetry approach within the density functional method at the B3LYP/def2-TZVP(-f)/def2-SVP level of theory.

Conversion of Nitric Oxide into Nitrous Oxide as Triggered by the Polarization of Coordinated NO by Hydrogen Bonding.

Reduction of the {Co(NO)}(8) cobalt-nitrosyl N-confused porphyrin (NCP) [Co(CTPPMe)(NO)] (1) produced electron-rich {Co(NO)}(9) [Co(CTPPMe)(NO)][Co(Cp*)2 ] (2), which was necessary for NO-to-N2 O conversion. Complex 2 was NO-reduction-silent in neat THF, but was partially activated to a hydrogen-bonded species 2⋅⋅⋅MeOH in THF/MeOH (1:1, v/v). This species coupling with 2 transformed NO into N2 O, which was fragmented from an [N2 O2 ]-bridging intermediate. An intense IR peak at 1622 cm(-1) was ascribed to ν(NO) in an [N2 O2 ]-containing intermediate. Time-course ESI(-) mass spectra supported the presence of the dimeric [Co(NCP)]2 (N2 O2 ) intermediate. Five complete NO-to-N2 O conversion cycles were possible without significant decay in the amount of N2 O produced.