Solid state structures of nonemitting complexes of cuprous iodide: (CuI(methylquinaldate))x (I), (CuI(isopropylquinaldate))2 (II) and (CuI(n-butylquinaldate))2 (III)

Tompkins, Jay A.; Maxwell, Jana L.; Holt, Elizabeth M.

doi:10.1016/s0020-1693(00)88356-5

Cited by 21 publications

(5 citation statements)

References 17 publications

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“…The two nitrogen atoms of Et 2 BCQEB Et are ∼5.41 Å apart in 16 , a substantial reduction compared to that in 15 (Δ N···N > 0.6 Å). Di( μ -iodo)dicopper(I) compounds supported by alkyl esters of quinaldic acid have similar geometric parameters …”

Section: Resultsmentioning

confidence: 99%

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Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

2003

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The syn coordination of histidine residues at the active sites of several carboxylate-rich non-heme diiron enzymes has been difficult to reproduce with small molecule model compounds. In this study, ligands derived from 1,8-naphthyridine, phthalazine, and 1,2-diethynylbenzene were employed to mimic this geometric feature. The preassembled diiron(II) complex [Fe(2)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(THF)(2)] (1), where Ar(Tol)CO(2)(-) is the sterically hindered carboxylate 2,6-di(p-tolyl)benzoate, served as a convenient starting material for the preparation of iron(II) complexes, all of which were crystallographically characterized. Use of the ligand 2,7-dimethyl-1,8-naphthyridine (Me(2)-napy) afforded the mononuclear complex [Fe(O(2)CAr(Tol))(2)(Me(2)-napy)] (2), whereas dinuclear [Fe(2)(micro-DMP)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(THF)] (3) resulted when 1,4-dimethylphthalazine (DMP) was employed. The dinuclear core of compound 3 is kinetically labile, as evidenced by the formation of [Fe(O(2)CAr(Tol))(2)(vpy)(2)] (4) upon addition of 2-vinylpyridine (vpy). The diiron analogue of 4, [Fe(2)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(vpy)(2)] (5), was prepared directly from 1. When the sterically more demanding ligand 2,6-di(4-tert-butylphenyl)benzoate (Ar(4-tBuPh)CO(2)(-)) was used, mononuclear [Fe(O(2)CAr(4)(-)(tBuPh))(2)(THF)(2)] (6) and [Fe(O(2)CAr(4)(-)(tBuPh))(2)(DMP)(2)] (7) formed. The difficulty in stabilizing a dinuclear core with these simple (N)(2)-donor ligands was circumvented by preparing a family of 1,2-diethynylbenzene-based ligands, from which were readily assembled the complexes [Fe(2)(Et(2)BCQEB(Et))(micro-O(2)CAr(Tol))(3)](OTf) (15) and [Cu(2)(Et(2)BCQEB(Et))(micro-I)(2)] (16), where Et(2)BCQEB(Et) is 1,2-bis(3-ethynyl-8-carboxylatequinoline)benzene ethyl ester. The Et(2)BCQEB(Et) framework provides both structural flexibility and the desired syn nitrogen donor geometry, thus serving as a good first-generation ligand in this class.

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Section: Resultsmentioning

confidence: 99%

“…Di(µ-iodo)dicopper-(I) compounds supported by alkyl esters of quinaldic acid have similar geometric parameters. 119…”

Section: Synthesis and Reactivity Of [Fe 2 (µ-Dmp)(µ-o 2 Car Tol ) 2 ...mentioning

confidence: 99%

Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

2003

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“…The first is metal-to-ligand charge transfer (MLCT) in the excited state, which is sensitive to the rigidity of the ligand. , The second is associated with high energy (HE) halide-to-ligand charge transfer (XLCT). The third is related to a lower energy (LE) mixed halide to metal charge transfer (XMCT), and finally, the fourth arises from cluster centered (CC) transfer. − Some authors have suggested that metal–metal interactions are crucial to the emission behavior and noted that LE is displayed only by those clusters with Cu···Cu distances less than 2.8 Å. , …”

Section: Introductionmentioning

confidence: 99%

“…12−14 Some authors have suggested that metal−metal interactions are crucial to the emission behavior and noted that LE is displayed only by those clusters with Cu•••Cu distances less than 2.8 Å. 15,16 Most studies published to date have been done at ambient conditions or at low and high temperatures, but rarely under pressure. Knowing the behavior of these materials under different environmental conditions is not only essential for commercial and technological applications.…”

Section: Introductionmentioning

confidence: 99%

Experimental and ab Initio Study of Catena(bis(μ₂-iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties

et al. 2016

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Copper(I) iodine compounds can exhibit interesting mechanochromic and thermochromic luminescent properties with important technological applications. We report the synthesis and structure determination by X-ray diffraction of a new polymeric staircase copper(I) iodine compound catena(bis(μ2-iodo)-6-methylquinoline-copper(I), [C10H9CuIN]. The structure is composed of isolated polymeric staircase chains of copper-iodine coordinated to organic ligands through Cu-N bonds. High pressure X-ray diffraction to 6.45 GPa shows that the material is soft, with a bulk modulus K0 = 10.2(2)GPa and a first derivative K'0 = 8.1(3), typical for organometallic compounds. The unit-cell compression is very anisotropic with the stiffest direction [302] arising from a combination of the stiff CuI ladders and the shear of the planar quinolone ligands over one another. Full structure refinements at elevated pressures show that pressures reduce the Cu···Cu distances in the compound. This effect is detected in luminescence spectra with the appearance of four sub-bands at 515, 600, 647, and 712 nm above 3.5 GPa. Red-shifts are observed, and they are tentatively associated with interactions between copper(I) ions due to the shortening of the Cu···Cu distances induced by pressure, below twice the van der Waals limit (2.8 Å). Additionally, ab initio simulations were performed, and they confirmed the structure and the results obtained experimentally for the equation of state. The simulation allowed the band structure and the electronic density of states of this copper(I) iodine complex to be determined. In particular, the band gap decreases slowly with pressure in a quadratic way with dEg/dP = -0.011 eV/GPa and d(2)Eg/dP(2) = 0.001 eV/GPa(2).

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“…Described here are photophysical and ab initio studies of some mononuclear copper(I) complexes of the type CuL n + , where L is a neutral nitrogen donor ligand. Mono- and polynuclear complexes of d 10 metal centers display remarkably rich luminescence and photophysical properties. − For example, the luminescence spectrum of the tetranuclear Cu(I) cluster Cu 4 I 4 (py) 4 ( A , py = pyridine), a copper tetrahedron face capped by iodines with a pyridine at each vertex, displays two emission bands (λ max em = 690 and 490 nm in ambient toluene) with different lifetimes (τ = 10.6 and 0.45 μs, respectively). − Ab initio calculations at the restricted Hartree−Fock self-consistent field (RHF-SCF) level demonstrated the lowest energy Franck−Condon excited state (ES) of A to be a roughly equal mix of Cu 4 I 4 “d → s” and halide-to-metal charge transfer (XMCT) character with the receptor “s” orbital in fact being a delocalized metal−metal bonding MO. We have termed this a “cluster centered” (CC) excited state .…”

Section: Introductionmentioning

confidence: 99%

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

1996

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Described are the photophysical properties of the mononuclear copper(I) complexes CuL(4)(+) (L = pyridine (py), 4-methylpyridine, 4-phenylpyridine, or acetonitrile), Cu(lut)(3)(+) (lut = 2,6-lutidine), and Cu(lut)(2)(+). Each of these compounds as their solid PF(6)(-) salts display a relatively long-lived (>1 &mgr;s), visible range emission at both ambient temperature and at 77 K but not in fluid solutions. Also reported are the results for ab initio calculations at the restricted Hartree-Fock self-consistent field level to probe the natures of lower energy excited states of the hypothetical species CuL(n)()(+) (L = NH(3), CH(3)CN, or py; n = 1-4). These results point to an assignment of the lowest energy, luminactive excited states as being largely metal centered, d --> s in character for each of the above complexes with the possible exception of the CuL(4)(+) species where L is py or a substituted analogue. In the case of Cu(py)(4)(+) the ab initiocalculations indicate a metal-to-ligand charge transfer to be the lowest energy Franck-Condon state, although the similarities of emission band shapes, energies, and lifetimes among the various complexes suggest a common d --> s assignment.

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Solid state structures of nonemitting complexes of cuprous iodide: (CuI(methylquinaldate))x (I), (CuI(isopropylquinaldate))2 (II) and (CuI(n-butylquinaldate))2 (III)

Cited by 21 publications

References 17 publications

Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

Experimental and ab Initio Study of Catena(bis(μ₂-iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

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Solid state structures of nonemitting complexes of cuprous iodide: (CuI(methylquinaldate))x (I), (CuI(isopropylquinaldate))2 (II) and (CuI(n-butylquinaldate))2 (III)

Cited by 21 publications

References 17 publications

Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

Modeling the Syn Disposition of Nitrogen Donors at the Active Sites of Carboxylate-Bridged Diiron Enzymes. Enforcing Dinuclearity and Kinetic Stability with a 1,2-Diethynylbenzene-Based Ligand

Experimental and ab Initio Study of Catena(bis(μ2-iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

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Product

Resources

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Experimental and ab Initio Study of Catena(bis(μ₂-iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties