The structure–function relationship, especially the origin of absorption and emission of light in carbon nanodots (CNDs), has baffled scientists. The multilevel complexity arises due to the large number of by-products synthesized during the bottom-up approach. By performing systematic purification and characterization, we reveal the presence of a molecular fluorophore, quinoxalino[2,3-b]phenazine-2,3-diamine (QXPDA), in a large amount (∼80% of the total mass) in red emissive CNDs synthesized from o-phenylenediamine (OPDA), which is one of the well-known precursor molecules used for CND synthesis. The recorded NMR and mass spectra tentatively confirm the structure of QXPDA. The close resemblance of the experimental vibronic progression and the mirror symmetry of the absorption and emission spectra with the theoretically simulated spectra confirm an extended conjugated structure of QXPDA. Interestingly, QXPDA dictates the complete emission characteristics of the CNDs; in particular, it showed a striking similarity of its excitation independent emission spectra with that of the original synthesized red emissive CND solution. On the other hand, the CND like structure with a typical size of ∼4 nm was observed under a transmission electron microscope for a blue emissive species, which showed both excitation dependent and independent emission spectra. Interestingly, Raman spectroscopic data showed the similarity between QXPDA and the dot structure thus suggesting the formation of the QXPDA aggregated core structure in CNDs. We further demonstrated the parallelism in trends of absorption and emission of light from a few other red emissive CNDs, which were synthesized using different experimental conditions.

Iron(V)-nitrido and -oxo complexes have been proposed as key intermediates in a diverse array of chemical transformations. Herein we present a detailed electronic-structure analysis of [Fe^V(N)(TPP)] (1, TPP^2– = tetraphenylporphyrinato), and [Fe^V(N)(cyclam-ac)]⁺ (2, cyclam-ac = 1,4,8,11-tetraazacyclotetradecane-1-acetato) using electron paramagnetic resonance (EPR) and ⁵⁷Fe Mössbauer spectroscopy coupled with wave function based complete active-space self-consistent field (CASSCF) calculations. The findings were compared with all other well-characterized genuine iron(V)-nitrido and -oxo complexes, [Fe^V(N)(MePy₂tacn)](PF₆)₂ (3, MePy₂tacn = methyl-N′,N″-bis(2-picolyl)-1,4,7-triazacyclononane), [Fe^V(N){PhB(t-BuIm)₃}]⁺ (4, PhB(^tBuIm)₃^– = phenyltris(3-tert-butylimidazol-2-ylidene)borate), and [Fe^V(O)(TAML)]⁻ (5, TAML^4– = tetraamido macrocyclic ligand). Our results revealed that complex 1 is an authenticated iron(V)-nitrido species and contrasts with its oxo congener, compound I, which contains a ferryl unit interacting with a porphyrin radical. More importantly, tetragonal iron(V)-nitrido and -oxo complexes 1–3 and 5 all possess an orbitally nearly doubly degenerate S = 1/2 ground state. Consequently, analogous near-axial EPR spectra with g_|| < g_⊥ ≤ 2 were measured for them, and their g_|| and g_⊥ values were found to obey a simple relation of g_⊥² + (2 – g_∥)² = 4. However, the bonding situation for trigonal iron(V)-nitrido complex 4 is completely different as evidenced by its distinct EPR spectrum with g_|| < 2 < g_⊥. Further in-depth analyses suggested that tetragonal low spin iron(V)-nitrido and -oxo complexes feature electronic structures akin to those found for complexes 1–3 and 5. Therefore, the characteristic EPR signals determined for 1–3 and 5 can be used as a spectroscopic marker to identify such highly reactive intermediates in catalytic processes.

The detailed mechanism of CO ₂ reduction by a cobalt( i ) complex is investigated using computations and kinetics.

Detailed electronic structure and its correlation with the intramolecular C-H amination reactivity of Fe-porphyrin-nitrene intermediates bearing different "axial" coordination have been investigated using multiconfigurational complete active space self-consistent field (CASSCF), N-electron valence perturbation theory (NEVPT2), and hybrid density functional theory (DFT-B3LYP) calculations. Three types of "axial" coordination, -OMe/-O(H)Me (1-Sul/2-Sul), -SMe/-S(H)Me (3-Sul/4-Sul), and -NMeIm (MeIm = 3-methyl-imidazole) (5-Sul) mimicking serine, cysteine, and histidine, respectively, along with no axial coordination (6-Sul) have been considered to decipher how the "axial" coordination of different strengths regulates the electronic integrity of the Fe-N core and nitrene-transfer reactivity of Fe-porphyrin-nitrene intermediates. CASSCF-based natural orbitals reveal two distinct classes of electronic structures: Fe-nitrenes (1-Sul and 3-Sul) with relatively stronger axial coordination (-OMe and -SMe) display "imidyl" nature and those (2-Sul, 4-Sul, and 6-Sul) with weaker axial coordination (-O(H)Me, -S(H)Me and no axial coordination) exhibit "imido-like" character. A borderline between the two classes is also observed with NMeIm axial coordination (5-Sul). Axial coordination of different strengths not only regulates the electronic structure but also modulates the Fe-3d orbital energies, as revealed through the d-d transition energies obtained by CASSCF/NEVPT2 calculations. The relatively lower energy of Fe-3d_z2 orbital allows easy access to low-lying high-spin quintet states in the cases of weaker "axial" coordination (2-Sul, 4-Sul, and 6-Sul), and the associated hydrogen atom transfer (HAT) reactivity appears to involve two-state triplet-quintet reactivity through minimum energy crossing point (^3,5MECP) between the spin states. In stark contrast, Fe-nitrenes with relatively stronger "axial" coordination (1-Sul and 3-Sul) undergo triplet-only HAT reactivity. Overall, this in-depth electronic structure investigation and HAT reactivity evaluation reveal that the weaker axial coordination in Fe-porphyrin-nitrene complexes (2-Sul, 4-Sul, and 6-Sul) can promote more efficient C-H oxidation through the quintet spin state.