Synthesis, structure, terahertz spectroscopy and luminescent properties of copper (I) complexes with bis(diphenylphosphino)methane and N-donor ligands

Fan, Weiwei; Li, Zhongfeng; Li, Jiao-Bao; Yang, Yuchen; Yuan, Yuan; Tang, Hung-Jie; Gao, Lingxiao; Jin, Qiong‐Hua; Zhang, Zhenwei; Zhang, Cunlin

doi:10.1016/j.molstruc.2015.06.066

Cited by 7 publications

(5 citation statements)

References 34 publications

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“…The ten [Cu(phen)(PP)] + and Cu(Bphen)(PP)] + complexes were investigated as powders, in CH 2 Cl 2 (298 and 77 K) and PMMA matrix (sample 1 wt %). The emission properties of some of these compounds have been already discussed, and our results confirm previous experimental findings, − ,,,,− (excluding those which misinterpreted the second harmonic of the excitation light as the emission of the complex). , …”

Section: Resultssupporting

confidence: 90%

“…To the best of our knowledge, the emission properties of at least six compounds out of the ten systematically investigated here have been discussed, at least in part, earlier, namely, [Cu(phen)(μ-dppm)] 2 2+ , − [Cu(phen)(dppe)] + , , [Cu(phen)(dppb)] + , , [Cu(phen)(POP)] + , − ,,, [Cu(Bphen)(dppb)] + , and [Cu(Bphen)(POP)] + . ,− The purpose of this paper is not just expanding the database of photoactive Cu(I) complexes available in the literature, but also providing a more comprehensive rationale of the structural, electronic, and luminescence properties of two selected classes of [Cu(NN)(PP)] + systems, in order to consolidate the general understanding of the electronic properties of this important class of coordination compounds.…”

Section: Introductionmentioning

confidence: 93%

“…The emission properties of some of these compounds have been already discussed, and our results confirm previous experimental findings, 23−25,27,35,47,49−52 (excluding those which misinterpreted the second harmonic of the excitation light as the emission of the complex). 42,49 All key data are gathered in Table S4 (solution and 77 K) and in Table 2 (solid state). In CH 2 Cl 2 solution, (faint) luminescence is observable only for the dinuclear complexes with dppm and the bulky POP chelator (Figure S11).…”

Section: Inorganic Chemistrymentioning

confidence: 99%

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Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties

et al. 2018

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The electronic and structural properties of ten heteroleptic [Cu(NN)(PP)]+ complexes have been investigated. NN indicates 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (Bphen); each of these ligands is combined with five PP bis-phosphine chelators, i.e., bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), and bis[(2-diphenylphosphino)phenyl] ether (POP). All complexes are mononuclear, apart from those based on dppm, which are dinuclear. Experimental dataalso taken from the literature and including electrochemical properties, X-ray crystal structures, UV–vis absorption spectra in CH2Cl2, luminescence spectra and lifetimes in solution, in PMMA, and as powdershave been rationalized with the support of density functional theory calculations. Temperature dependent studies (78–358 K) have been performed for selected complexes to assess thermally activated delayed fluorescence. The main findings are (i) dependence of the ground-state geometry on the crystallization conditions, with the same complex often yielding different crystal structures; (ii) simple model compounds with imposed C 2v symmetry ([Cu(phen)(PX3)2]+; X = H or CH3) are capable of modeling structural parameters as a function of the P–Cu–P bite angle, which plays a key role in dictating the overall structure of [Cu(NN)(PP)]+ complexes; (iii) as the P–Cu–P angle increases, the energy of the metal-to-ligand charge transfer absorption bands linearly increases; (iv) the former correlation does not hold for emission spectra, which are red-shifted for the weaker luminophores; (v) the larger the number of intramolecular π-interactions within the complex in the ground state, the higher the luminescence quantum yield, underpinning a geometry locking effect that limits the structural flattening of the excited state. This work provides a general framework to rationalize the structure–property relationships of [Cu(NN)(PP)]+, a class of compounds of increasing relevance for electroluminescent devices, photoredox catalysis, and solar-to-fuels conversion, which so far have been investigated in an unsystematic fashion, eluding a comprehensive understanding.

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Section: Resultssupporting

confidence: 90%

Section: Introductionmentioning

confidence: 93%

Section: Inorganic Chemistrymentioning

confidence: 99%

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Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties

et al. 2018

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“…The stretching of C=C bonds occurs in the range of 1600-1450 cm −1 , while the out-of-plane angular deformation of the =C-H bond can be observed between 900 and 690 cm −1 . Complexes 1-4 exhibit vibrational modes between 540 and 430 cm −1 , corresponding to the typical P-C Aromatic bonds of the triphenylphosphine ligand and Cu-P bonds [44][45][46]. Figures S1-S4 show the spectra of all complexes showing these vibrational modes.…”

Section: Structural Studiesmentioning

confidence: 99%

Copper(I)/Triphenylphosphine Complexes Containing Naphthoquinone Ligands as Potential Anticancer Agents

Leite,

Araujo-Neto,

Guedes

et al. 2023

Inorganics

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Four new Cu/PPh3/naphtoquinone complexes were synthesized, characterized (IR, UV/visible, 1D/2D NMR, mass spectrometry, elemental analysis, and X-ray diffraction), and evaluated as anticancer agents. We also investigated the reactive oxygen species (ROS) generation capacity of complex 4, considering the well-established photochemical property of naphthoquinones. Therefore, employing the electron paramagnetic resonance (EPR) “spin trap”, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) technique, we identified the formation of the characteristic •OOH species (hydroperoxyl radical) adduct even before irradiating the solution containing complex 4. As the irradiation progressed, this radical species gradually diminished, primarily giving rise to a novel species known as •DMPO-OH (DMPO + •OH radical). These findings strongly suggest that Cu(I)/PPh3/naphthoquinone complexes can generate ROS, even in the absence of irradiation, potentially intensifying their cytotoxic effect on tumor cells. Interpretation of the in vitro cytotoxicity data of the Cu(I) complexes considered their stability in cell culture medium. All of the complexes were cytotoxic to the lung (A549) and breast tumor cell lines (MDA-MB-231 and MCF-7). However, the higher toxicity for the lung (MRC5) and breast (MCF-10A) non-tumoral cells resulted in a low selectivity index. The morphological analysis of MDA-MB-231 cells treated with the complexes showed that they could cause decreased cell density, loss of cell morphology, and loss of cell adhesion, mainly with concentrations higher than the inhibitory concentration of 50% of cell viability (IC50) values. Similarly, the clonogenic survivance of these cells was affected only with concentrations higher than the IC50 values. An antimigratory effect was observed for complexes 1 and 4, showing around 20–40% of inhibition of wound closure in the wound healing experiments.

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“…Rather, it has a tendency to act as either a monodentate (η 1 -dppm) or bridging bidentate ligand (µ 2 -dppm) [18]. Many examples The Cu(I)-dppm complexes are emerging class of polynuclear complexes, that are drawing considerable attention because of their photophysical properties [19][20][21][22] and prospective use as a catalyst [23][24][25] and a sensor for various organic bases [26] and anions [27]. Binuclear Cu(I) species possess an enhanced reactivity toward organic azides in copper-catalysed azide-alkyne cycloaddition compared to monomeric copper complexes [28][29][30][31][32][33][34][35].…”

Section: Introductionmentioning

confidence: 99%

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

et al. 2017

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Bis(diphenylphosphino)methane copper(I) tetrahydroborate was synthesized by ligands exchange in bis(triphenylphosphine) copper(I) tetrahydroborate, and characterized by XRD, FTIR, NMR spectroscopy. According to XRD the title compound has dimeric structure, [(µ 2 -dppm) 2 Cu 2 (η 2 -BH 4 ) 2 ], and crystallizes as CH 2 Cl 2 solvate in two polymorphic forms (orthorhombic, 1, and monoclinic, 2) The details of molecular geometry and the crystal-packing pattern in polymorphs were studied. The rare Twisted Boat-Boat conformation of the core Cu 2 P 4 C 2 cycle in 1 is found being more stable than Boat-Boat conformation in 2.

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Synthesis, structure, terahertz spectroscopy and luminescent properties of copper (I) complexes with bis(diphenylphosphino)methane and N-donor ligands

Cited by 7 publications

References 34 publications

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties

Copper(I)/Triphenylphosphine Complexes Containing Naphthoquinone Ligands as Potential Anticancer Agents

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

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