Cu-N Bond Research Articles

Impact of the RF Power on the Copper Nitride Films Deposited in a Pure Nitrogen Environment for Applications as Eco-Friendly Solar Absorber

This material can be considered to be an interesting eco-friendly choice to be used in the photovoltaic field. In this work, we present the fabrication of Cu3N thin films by reactive radio-frequency (RF) magnetron sputtering at room temperature, using nitrogen as the process gas. Different RF power values ranged from 25 to 200 W and gas pressures of 3.5 and 5 Pa were tested to determine their impact on the film properties. The morphology and structure were exhaustively examined by Atomic Force Microscopy (AFM), Fourier Transform Infrared (FTIR) and Raman Spectroscopies and X-ray Diffraction (XRD), respectively. The AFM micrographs revealed different morphologies depending on the total pressure used, and rougher surfaces when the films were deposited at the lowest pressure; whereas FTIR and Raman spectra exhibited the characteristics bands related to the Cu-N bonds of Cu3N. Such bands became narrower as the RF power increased. XRD patterns showed the (100) plane as the preferred orientation, that changed to (111) with the RF power, revealing a worsening in structural quality. Finally, the band gap energy was estimated from transmission spectra carried out with a Perkin Elmer 1050 spectrophotometer to evaluate the suitability of Cu3N as a light absorber. The values obtained demonstrated the capability of Cu3N for solar energy conversion applications, indicating a better film performance under the sputtering conditions 5.0 Pa and RF power values ranged from 50 to 100 W.

Mechanistic insights into CO2 conversion chemistry of copper bis-(terpyridine) molecular electrocatalyst using accessible operando spectrochemistry

The implementation of low-cost transition-metal complexes in CO2 reduction reaction (CO2RR) is hampered by poor mechanistic understanding. Herein, a carbon-supported copper bis-(terpyridine) complex enabling facile kilogram-scale production of the catalyst is developed. We directly observe an intriguing baton-relay-like mechanism of active sites transfer by employing a widely accessible operando Raman/Fourier-transform infrared spectroscopy analysis coupled with density functional theory computations. Our analyses reveal that the first protonation step involves Cu-N bond breakage before the *COOH intermediate forms exclusively at the central N site, followed by an N-to-Cu active site transfer. This unique active site transfer features energetically favorable *CO formation on Cu sites, low-barrier CO desorption and reversible catalyst regeneration, endowing the catalyst with a CO selectively of 99.5 %, 80 h stability, and a turn-over efficiency of 9.4 s−1 at −0.6 V vs. the reversible hydrogen electrode in an H-type cell configuration. We expect that the approach and findings presented here may accelerate future mechanistic studies of next-generation CO2RR electrocatalysts.

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions.

The long-term stability of single-atom catalysts is a major factor affecting their large-scale commercial application. How to evaluate the dynamic stability of single-atom catalysts under working conditions is still lacking. Here, taking a single copper atom embedded in N-doped graphene as an example, the "constant-potential hybrid-solvation dynamic model" is used to evaluate the reversible transformation between copper single atoms and clusters under realistic reaction conditions. It is revealed that the adsorption of H is a vital driving force for the leaching of the Cu single atom from the catalyst surface. The more negative the electrode potential, the stronger the adsorption of H. As a result, the competitive hydrogen evolution reaction is inhibited, and Cu-N bonds are weakened, resulting in some Cu atoms being tethered on the catalyst surface and some being dissolved in the aqueous solution. The collision of the Cu atoms in the two states forms a transient Cu cluster structure as a true catalytic active site to promote CO2 reduction to ethanol. As the applied potential is released or switched to a positive value, hydroxyl radicals (OH•) play a dominant role in the oxidation process of the Cu cluster, and then Cu returns to the initial atomic dispersion state by redeposition, completing the reconstruction cycle of the copper catalyst. Our work provides a fundamental understanding of the dynamic stability of Cu single-atom catalysts under working conditions at the atomic level and calls for a reassessment of the stability of currently reported single-atom catalysts considering realistic reaction conditions.

Oxidation of Cu3N thin films obtained from Cu annealed under NH3:O2 flow: A Raman and N-K-edge NEXAFS study

Cu3N layers prepared by annealing, under NH3:O2 flow, of Cu sputtered on Si, fused SiO2, and soda-lime-glass were studied by Raman and N-K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The annealing temperatures were ranging from 300° to 800°C. Benefiting from resonance effects on the Raman peak intensities when different excitation wavelengths are used, the contribution in the Raman signal of copper oxides, which provide peaks lying close to those of Cu3N, is more easily discriminated. The formation of Cu2O surface oxide is observed in almost all the samples even for annealing at low temperatures. CuO is generally formed at higher temperatures with the onset depending on the amount of O2 in the NH3:O2 mixture. However, high temperature is necessary to grow larger crystallites, as it is deduced from the decrease in the width of the high-frequency Raman peak (at ca. 650 cm−1) of Cu3N, in accordance with Scanning Electron Microscopy observations. The formation of CuO is accompanied by the creation of N2 trapped in the sample, which is directly detected by the NEXAFS measurements. N2 is most probably formed by the N atoms originating from the dissociation of the Cu-N bonds.

Crystallographic studies of fac- and mer-isomers of Cu[1,4,7,10,13,16-hexaazacyclooctadecane]2+. Influence of counterion and crystallization solvent on crystal structure and dynamic Jahn-Teller effects. Computational studies of structures, energetics, and mechanism of mer-fac isomerization

The syntheses and crystal structures of mer- and fac-isomers of [Cu(18N6)]2+(X−)2 are reported (18 N6 = 1,4,7,10,13,16-hexaazacyclooctadecane; X− = BF4−, ClO4−, NO3−) and compared to a previously reported example (X− = Cl−). Solution structures of the [Cu(18N6)]2+ dication in MeNO2 or MeOH are shown by FT-IR to be almost exclusively mer, and simple evaporation of these solutions or crystallization using Et2O co-solvent also afford the solid mer-salts. However, using C6H6 or CCl4 as crystallization co-solvents afforded the corresponding fac-isomers of the BF4− and ClO4− salts, in which the anions and the symmetrical solvent occupy locations on the crystallographic 3-fold axis. Similar treatment of the less symmetrical NO3− salts affords the mer-isomer without inclusion of C6H6. The solid-state structures of the mer-isomers each exhibit the anticipated tetragonal Jahn-Teller distortions, with two longer Cu-N bonds. In contrast the fac-isomers all show internally identical Cu-N distances, due to a dynamic exchange between Jahn-Teller distorted structures in the crystal. Density Functional Theory (DFT) is used to provide rationalizations of these observations and to elucidate an energetically feasible mechanistic pathway for the facile interconversion of mer and fac isomers in solution.

Evaluation of the Crystal Structure and Mechanical Properties of Cu Doped TiN Films

In this study, TiN films doped with different copper contents (TiCuN) were prepared by using direct current magnetron sputtering method. The effects of Cu doping on composition, structure, and mechanical properties of TiN films were studied by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), a Vickers microhardnessmeter, and density functional theory (DFT). The results of experimental and DFT study showed that Cu mainly replaced Ti atoms in TiN to form replacement solid solution doping. When Cu replaced Ti in TiN, a weak Cu-N (bond population varied from 0.06 to 0.11) covalent bond formed; meanwhile, the bonding strength of Ti-N (bond population varied from 0.29 to 0.4) bond adjacent to Cu increased. When Cu content was low, a small number of weak Cu-N bonds were formed, with strengthened Ti-N bond near Cu atom, resulting in an increased hardness of Cu doped TiN films. According to the theory of weak bonds, when the Cu content was increased further, the number of weak Cu-N bonds increased and TiCuN hardness decreased. With an increase in Cu content, it was found the toughness of TiCuN also increased. The results of this study will provide a theoretical and experimental guidance for improving the toughness and deformation resistance of TiN, which has a potential application in the surface modification of medical devices.

Passiflora edulia Sims leaves Extract as renewable and degradable inhibitor for copper in sulfuric acid solution

In this research, we obtained Passiflora edulia Sims leaves Extract (PESLE) using a simple and green pure water extraction method. Experiment and theoretical calculations data show that PESLE can effectually restrain Cu corrosion in H2SO4 medium. Electrochemical results demonstrate that the PESLE is 800 mg/L, its anti-corrosion nature can reach about 96%. And with the augment of temperature, the anti-corrosion capacity of PESLE can still reach about 95% at a temperature of 318 K. SEM and AFM morphology test data show that PESLE is adsorbed onto the copper interface, the copper sample is effectively protected and the surface becomes relatively flat. The morphology test results directly prove that PESLE efficaciously restrain the corrosion of Cu in H2SO4 environment. XPS test results show that PESLE adsorption onto the Cu interface can detect Cu-N bond, which proves that chemical adsorption occurs. Quantum chemistry calculation data manifest that the three components of PESLE can reveal high anti-corrosion property. Molecular dynamics simulation data manifest the three components of PESLE can be adsorbed at the Cu (111) surface with paralleled way, and can have a large binding energy.

Composite complex agent based on organic amine alkali for BTA removal in post CMP cleaning of copper interconnection

The combination of FA/OII chelating agent and double complexing agent ammonium citrate can shift the ionization to the right (the dissolution of Cu-BTA), effectively break the Cu-N bond, and accelerate BTA removal on the copper surface. • Ammonium citrate's nucleophilic attack may occur near C2 and O4 atoms. • The electrophilic attack may occur near N22 and N26 atoms. • The pH value of the cleaning solution is stable at 10.24 for optimal removal of BTA. • Effect and mechanism of composite complex agent were studied by electrochemical, contact angle, SEM, FTIR and XPS. • Composite complex agent can complex copper ions, form copper amine complex and break the ionization balance of Cu-BTA. Benzotriazole (BTA) is a common corrosion inhibitor in chemical mechanical polishing (CMP). It is also the main pollutant to be removed in post CMP cleaning. In this paper, a new type of alkaline cleaning solution based on composite complexing agent was proposed for BTA removal. The optimal concentration and pH value of the cleaning solution were explored using electrochemical measurement and contact angle measurement. When the components were 200 ppm FA/OII chelating agent and 0.1 vol% ammonium citrate (pH = 10.24), BTA residue on copper surface can be effectively removed. Density Functional Theory (DFT) proved that ammonium citrate's nucleophilic attack may occur around C2 and O4 atoms, respectively. The electrophilic attack of ammonium citrate may occur around N22 and N26 atoms, respectively. The results of scanning electron microscopy (SEM) showed that a lower surface roughness was obtained after cleaning. Fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectroscopy (XPS) measurements confirmed that the cleaning solution could complex copper ions, break the ionization balance of Cu-BTA and accelerate its dissolution, so as to remove BTA effectively.

Facilitating Redox Cycles of Copper Species by Pollutants in Peroxymonosulfate Activation.

The redox behavior of metal active sites determines the rate of heterogeneous catalysis in peroxymonosulfate activation. Previous reports focused on the construction of catalysts for accelerating interfacial electron transfer. In this work, a new strategy was proposed for facilitating valence cycles of Cu+/Cu2+ by using pollutants. The 2.5Cu/CeO2/PMS system was capable of achieving the efficient removal of pollutants, including tetracycline, oxytetracycline, and rhodamine B, in a wide pH working range. In the presence of tetracycline, a Cu-N bond was formed between the -NH2 group of tetracycline and the Cu site of the catalyst, showing that the coordination of Cu active sites changed to CuO4N1. The charge of CuO4N1 active sites rearranged, making it easier to obtain electrons and promote the PMS oxidation, thereby accelerating the reduction of Cu2+ to Cu+ and PMS activation. The PMS activation system showed excellent sustainability and selectivity for the removal of organic pollutants. This study provides a novel routine to promote peroxymonosulfate activation by utilizing pollutants to accelerate the redox behavior of metal species.

Carbon nitride nanotubes anchored with high-density CuNx sites for efficient degradation of antibiotic contaminants under photo-Fenton process: Performance and mechanism

The low specific surface area, poor porosity, and weak charge transport caused by the disordered morphology of metal-N-site catalysts are the main factors limiting their environmental applications. Therefore, a hollow-nanotube carbon nitride (Cu-HNCN) catalyst with CuNx sites dispersed in a hollow nanotube-like CN was constructed and used for the degradation of organic pollutants via the photo-Fenton (PF) process. The high specific surface area, rich porosity, and good visible-light trapping capability of the Cu-HNCN nanotubes were identified. The Cu-HNCN/PF system achieved 96.0% degradation efficiency of tetracycline within 50 min and showed efficient degradation of various antibiotic contaminants. Moreover, the short Cu-N bonds contributed to the improved stability and decreased copper leaching in the Cu-HNCN/PF system. Cu-HNCN, with its enhanced photogenerated charge generation, separation, and transport, was the key to the generation of abundant active species and efficient degradation of pollutants. In addition, frontier electron density theory successfully distinguished the roles of different types of active species in the degradation process. This work provides new insights into the development of catalysts with high stability and accelerated electron transfer to enhance the application of the PF process in practical wastewater purification.

Synthesis, characterization of some Cu(II) complexes of 1,2,4-triazine ligands and their evaluation as antimicrobial and antioxidant agent

Three Cu(II) complexes of as-triazines; 3-(2-Py)-5,6-diphenyl-1,2,4-triazine (PDT), 3-(2-Py)-5,6-bis-(p-methoxyphenyl)-1,2,4-triazine (PBMPT) and 3-(2-Py)-5,6-bis(4-biphenyl)-1,2,4-triazine (PBBT) have been synthesized and characterized by elemental analysis, complexometric method, thermogravimetric analysis, FTIR, UV–Vis spectroscopy, magnetic susceptibility measurements, scanning electron microscopy, X-ray powder diffraction studies, and conductivity measurements. FTIR spectroscopic data have confirmed the existence of Cu-N and Cu-O bonds in all three complexes as well as stretching frequencies of N = N and C = N complexes have been shifted towards lower frequencies in comparison with that of the ligands. In UV–Vis spectra, a bathochromic shift has been observed for the complexes due to variations in substituents in as-triazine ligands. Molar conductance measurement confirmed the non-electrolytic nature of the complexes. From the values of magnetic moment measurements, it can be concluded that all complexes belong to distorted octahedral geometry, and as-triazines act as a bidentate ligand and coordinate with the metal ion via nitrogen atoms of triazine and pyridine moiety respectively. Since metallotriazine complexes possess interesting biological and medicinal properties; antimicrobial and antioxidant properties of these as-triazine-copper(II) complexes were also studied. The results from antimicrobial studies show that all the complexes and as-triazines except PDT itself possess high antimicrobial activity. All the three synthesized complexes showed significant antioxidant DPPH radical scavenging activity with IC50 values in the range of 20–30 µg/mL.

An efficient solid-liquid interface adsorption mode in chalcopyrite flotation with a novel di-minerophilic group surfactant 5-methyl isobutylxanthate-1,3,4-oxadiazole-2-thione

A novel chelating collector containing di-minerophilic group named 5-methyl isobutylxanthate-1,3,4-oxadiazole-2-thione (MIXODT) was first prepared and used for chalcopyrite flotation in this article. The flotation behavior of chalcopyrite with MIXODT as a collector was first evaluated by the micro-flotation experiments, and the results indicated that MIXODT showed better flotation capacity than sodium isobutyl xanthate (SIBX) for chalcopyrite recovery under acidic circumstances. Then hydrophobic mechanism of chalcopyrite was evaluated by wettability measurements, ζ-potential, interaction of MIXODT with metal ions, FTIR spectra and X-ray photoelectron spectroscopy (XPS). The wettability measurements proved that the surface hydrophobicity of chalcopyrite was improved significantly after MIXODT treatment. ζ-potential indicated that MIXODT chemisorbed on chalcopyrite surfaces. The experiment result of MIXODT with copper ions suggested that MIXODT had chemical interaction with Cu+ and Cu2+ ions. Moreover, FTIR and XPS spectra illustrated that the MIXODT-Cu complex was formed on chalcopyrite surface under the action of Cu-S and Cu-N bonds, accompanied with reduction of partial surface Cu(II) to Cu(I). Further, two different adsorption models of MIXODT-Cu+ and MIXODT-Cu2+ with “H” and “♬” types were proposed and predicted by DFT calculation respectively.

Revealing the Underestimated Anticancer Effect of Azurin by Mechanical Unfolding.

As a potential anticancer agent, azurin has attracted extensive attraction among chemists, physicists, and material scientists. Its structural and unfolding/folding information has been partially understood, but some detailed information, such as the difference in the unfolding processes between apo-azurin and holo-azurin, the mechanical stability, and the role of the copper cluster in its stability, has not been addressed adequately, especially at the single-molecule level. Here, we employed AFM-based single-molecule force spectroscopy to investigate the unfolding process of azurin in the apo and holo forms under an external force. The results indicated that the unfolding processes of apo-azurin and holo-azurin are different, and holo-azurin requires a stronger force to unfold than does apo-azurin. The copper cluster exhibited a more significant impact on the stability and the folding process of holo-azurin: the copper cluster was completely broken, and the copper ion left the unfolded azurin during the unfolding process of azurin. We suspected that the presence of the disulfide bond in azurin made the unfolding of the copper cluster different from that in pseudoazurin, which is also a type I copper protein like azurin. Rarely reported in previous studies, the mechanical strength of the Cu-N(His) bond of the copper cluster was obtained in this study, which is weaker than that of most metal-S(Cys) bonds but higher than that of the Fe-N(His) bond. Altogether, our results offer a possible new scenario for azurin to widely extend its anticancer activity.

Monodisperse Cu Cluster-Loaded Defective ZrO2 Nanofibers for Ambient N2 Fixation to NH3.

Electrocatalytic nitrogen reduction to ammonia has attracted increasing attention as it is more energy-saving and eco-friendly. For this endeavor, the development of high-efficiency electrocatalysts with excellent selectivity and stability is indispensable to break up the stable covalent triple bond in nitrogen. In this study, we report monodisperse Cu clusters loaded on defective ZrO2 nanofibers for nitrogen reduction under mild conditions. Such an electrocatalyst achieves an NH3 yield rate of 12.13 μg h-1 mgcat.-1 and an optimal Faradaic efficiency of 13.4% at -0.6 V versus the reversible hydrogen electrode in 0.1 M Na2SO4. Density functional theory calculations reveal that the N2 molecule was reduced to NH3 at the Cu active site with an ideal overpotential. Meanwhile, the interaction between bonding and antibonding of the Cu-N bond promotes activation of N2 and maintains a low desorption barrier.

Quantum chemical exploration on the inhibition performance of indole and some of its derivatives against copper corrosion

The inhibitory behavior of indole and some of its derivatives and their conformers against copper corrosion was studied by density functional theory (DFT) and molecular dynamics simulations. The calculated reactivity parameters based on the values of EHOMO, ELUMO, energy gap (ΔEgap), hardness (η), softness (σ), electronegativity (χ), electrophilicity (ω), Fukui indices (fk), fraction of electron transferred (ΔN) and back-donation of electrons (ΔEback-d) between the inhibitors and the copper surface have been scrutinized. DFT-molecular dynamics simulations have been used to investigate the adsorption mechanism for neutral and deprotonated forms of inhibitors. It was established that the carbonyl and carboxylic groups of the indole derivatives have a great effect on the inhibition efficiency. The results of molecular reactivity indicate that the inhibition efficiency is ranked as follows: indole < IND3-C2 < IND3-C1 < IND5-C1 < IND2-C2 < IND2-C1 < IND5-C2 < isatin. Neutral inhibitors physisorb to the copper surface except for isatin, which is chemisorbed due to its higher binding energy and its increased amount of charge transfer. The deprotonated inhibitors are chemisorbed on Cu(111) surface by establishing strong covalent CuN bonds, as supported by charge density difference analysis.

Cu[Ni(2,3-pyrazinedithiolate)2] Metal-Organic Framework for Electrocatalytic Hydrogen Evolution.

The application of metal-organic frameworks (MOFs) as electrocatalysts for small molecule activation has been an emerging topic of research. Previous studies have suggested that two-dimensional (2D) dithiolene-based MOFs are among the most active for the hydrogen evolution reaction (HER). Here, a three-dimensional (3D) dithiolene-based MOF, Cu[Ni(2,3-pyrazinedithiolate)2] (1), is evaluated as an electrocatalyst for the HER. In pH 1.3 aqueous electrolyte solution, 1 exhibits a catalytic onset at -0.43 V vs the reversible hydrogen electrode (RHE), an overpotential (η10 mA/cm2) of 0.53 V to reach a current density of 10 mA/cm2, and a Tafel slope of 69.0 mV/dec. Interestingly, under controlled potential electrolysis, 1 undergoes an activation process that results in a more active catalyst with a 200 mV reduction in the catalytic onset and η10 mA/cm2. It is proposed that the activation process is a result of the cleavage of Cu-N bonds in the presence of protons and electrons. This hypothesis is supported by various experimental studies and density functional theory calculations.

Copper–Ligand Cooperativity in H2 Activation Enables the Synthesis of Copper Hydride Complexes

Copper(I) complexes of a new participative triphosphane ligand (2 H) have been prepared and structurally characterized, in particular [Cu(2 H)I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2 H)(HBEt3)]. Their formation evidences transient formation of [Cu(2 H)H] formed by hydrogenolysis of the Cu-N bond of [Cu(2)]2. [Cu(2 H)(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2 H)(O2CH)]. QTAIM analysis of the Cu-H-BEt3 interaction indicates a hydride complex stabilized by the Lewis acid BEt3.

New Volatile Perfluorinated Amidine-Carboxylate Copper(II) Complexes as Promising Precursors in CVD and FEBID Methods.

In the present study, we have synthesised and characterised newly copper(II) complexes with the general formula [Cu2(NH2(NH=)CC2F5)2(µ–O2CRF)4], where RF = CF3, C2F5, C3F7, C4F9. Infrared spectroscopy, mass spectrometry with electron ionisation (EI MS), and density-functional theory (DFT) calculations were used to confirm compounds’ composition and structure. The volatility of the compounds was studied using thermal analysis (TGA), EI MS mass spectrometry, variable temperature infrared spectroscopy (VT IR), and sublimation experiments. Research has revealed that these compounds are the source of metal carriers in the gas phase. The thermal decomposition mechanism over reduced pressure was proposed. TGA studies demonstrated that copper transfer to the gaseous phase occurs even at atmospheric pressure. Two selected complexes [Cu2(NH2(NH=)CC2F5)2(µ–O2CC2F5)4] and [Cu2(NH2(NH=)CC2F5)2(µ–O2CC3F7)4] were successful used as chemical vapour deposition precursors. Copper films were deposited with an evaporation temperature of 393 K and 453 K, respectively, and a decomposition temperature in the range of 573–633 K without the use of hydrogen. The microscopic observations made to investigate the interaction of the [Cu2(NH2(NH=)CC2F5)2(µ–O2CC2F5)4] with the electron beam showed that the ligands are completely lost under transmission electron microscopy analysis conditions (200 keV), and the final product is copper(II) fluoride. In contrast, the beam energy in scanning electron microscopy (20 keV) was insufficient to break all coordination bonds. It was shown that the Cu-O bond is more sensitive to the electron beam than the Cu-N bond.

Comparison Study of Synthesized Red (or Blood) Orange Peels and Juice Extract-Nanoflowers and Their Antimicrobial Properties on Fish Pathogen (Yersinia ruckeri).

In this work, we synthesized blood orange peel extract-copper (II) (Cu2+) ions nanoflower (NFs) and blood orange juice extract-copper (II) (Cu2+) ions nanoflower examine their antimicrobial properties on the fish pathogen (Yersinia ruckeri). The main compounds of the blood orange peel extract and the blood orange juice extract were organic components, and the copper (II) (Cu2 +) ions were inorganic components. BOPE-Cu2 + nanoflowers are quite compact, porous, and uniform as compared to BOJE-Cu2+ nanoflowers. Scanning Electron Microscopy, Fourier Transform Infrared spectrometry, and Energy-Dispersive X-ray spectroscopy were used to observe the structures of the NFs. The findings of FT-IR show Cu-O and Cu-N bonds in NF, which may be an indicator of the development of NFs. Although the antimicrobial actions of BOPE-hNFs and BOJE-hNFs against Yersinia ruckeri (NCTC 12,268) have been confirmed.

Substituent effects on the photophysical properties of 2,9-substituted phenanthroline copper(I) complexes: a theoretical investigation.

The electronic and nuclear structures of a series of [Cu(2,9-(X)2 -phen)2 ]+ copper(I) complexes (phen=1,10-phenanthroline; X=H, F, Cl, Br, I, Me, CN) in their ground and excited states are investigated by means of density functional theory (DFT) and time-dependent (TD-DFT) methods. Subsequent Born-Oppenheimer molecular dynamics is used for exploring the T1 potential energy surface (PES). The T1 and S1 energy profiles, which connect the degenerate minima induced by ligand flattening and Cu-N bond symmetry breaking when exciting the molecule are calculated as well as transition state (TS) structures and related energy barriers. Three nuclear motions drive the photophysics, namely the coordination sphere asymmetric breathing, the well-documented pseudo Jahn-Teller (PJT) distortion and the bending of the phen ligands. This theoretical study reveals the limit of the static picture based on potential energy surfaces minima and transition states for interpreting the luminescent and TADF properties of this class of molecules. Whereas minor asymmetric Cu-N bonds breathing accompanies the metal-to-ligand-charge-transfer re-localization over one or the other phen ligand, the three nuclear movements participate to the flattening of the electronically excited complexes. This leads to negligible energy barriers whatever the ligand X for the first process and significant ligand dependent energy barriers for the formation of the flattened conformers. Born-Oppenheimer (BO) dynamics simulation of the structural evolution on the T1 PES over 11 ps at 300 K confirms the fast backwards and forwards motion of the phenanthroline within 200-300 fs period and corroborates the presence of metastable C2 structures.