Solid state coordination chemistry of the copper cyanide–organoamine system: hydrothermal synthesis and structural characterization of [{Cu2(bpy)2(CN)}2Cu5(CN)7]·0.17H2O

Chesnut, Douglas J.; Kusnetzow, Anakarin; Zubieta, Jon

doi:10.1039/a806500d

Cited by 55 publications

(28 citation statements)

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“…All Cu atoms are connected by μ 2 -bridging cyano ligands, forming simple 2D sheets composed of elongated fused hexagonal {Cu 8 (CN) 8 } rings. This and closely related motifs have been observed previously [51,55,58,59]. The rings are stacked such that trigonal Cu2 lies almost directly above linear Cu1, the shortest interplanar Cu⋯Cu distance being 3.076 Å and, thus, without metallophilic interactions.…”

Section: Resultssupporting

confidence: 81%

“…Selected bond lengths and bond angles are given in Figures 1, 3 and Figure 4, and in the Supplementary Materials. While the Me 4 N + cyanocuprate(I) complexes herein are the first reported salts of this cation, cyanocuprates are known for other cations including alkylammonium [50,51,52,53,54,55,56], phosphonium ions [57], alkali metal ions [58], and copper(II) ions [54,55,59,60,61,62,63,64,65], and protonated water or methanol [60,66]. In all cases, 2D or 3D anionic networks result from bridging of the cyano ligands.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

et al. 2019

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The structures of three tetramethylammonium cyanocuprate(I) 3D networks [NMe4]2[Cu(CN)2]2•0.25H2O (1), [NMe4][Cu3(CN)4] (2), and [NMe4][Cu2(CN)3] (3), (Me4N = tetramethylammonium), and the photophysics of 1 and 2 are reported. These complexes are prepared by combining aqueous solutions of the simple salts tetramethylammonium chloride and potassium dicyanocuprate. Single-crystal X-ray diffraction analysis of complex 1 reveals {Cu2(CN)2(μ2-CN)4} rhomboids crosslinked by cyano ligands and D3h {Cu(CN)3} metal clusters into a 3D coordination polymer, while 2 features independent 2D layers of fused hexagonal {Cu8(CN)8} rings where two Cu(I) centers reside in a linear C∞v coordination sphere. Metallophilic interactions are observed in 1 as close Cu⋯Cu distances, but are noticeably absent in 2. Complex 3 is a simple honeycomb sheet composed of trigonal planar Cu(I) centers with no Cu…Cu interactions. Temperature and time-dependent luminescence of 1 and 2 have been performed between 298 K and 78 K and demonstrate that 1 is a dual singlet/triplet emitter at low temperatures while 2 is a triplet-only emitter. DFT and TD-DFT calculations were used to help interpret the experimental findings. Optical memory experiments show that 1 and 2 are both optical memory active. These complexes undergo a reduction of emission intensity upon laser irradiation at 255 nm although this loss is much faster in 2. The loss of emission intensity is reversible in both cases by applying heat to the sample. We propose a light-induced electron transfer mechanism for the optical memory behavior observed.

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Section: Resultssupporting

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

et al. 2019

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“…Noteworthy, the cyclic structures are predicted to be more stable than the corresponding linear ones by 12 up to 65 kcal/mol; the stability increases as the ring size increases. It is important to notice that anionic 2‐D nets of alternating fused rows of pseudohexagonal [CuCN] 6 rings and six‐sided [CuCN] 8 rings were characterized by X‐ray crystal structure determination of the products of hydrothermal reactions of the copper‐cyano‐organoamine system . Four‐member [CuCN] 4 and twelve‐member [CuCN] 12 rings were also observed in the products of hydrothermal reactions of the copper‐cyano‐organoamine system .…”

Section: Resultsmentioning

confidence: 99%

Electronic, bonding, and optical properties of 1d [CuCN]_n (n = 1–10) chains, 2d [CuCN]_n (n = 2–10) nanorings, and 3d [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods

Tsipis

Stalikas

2015

J Comput Chem

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The electronic, bonding, and photophysical properties of one-dimensional [CuCN](n) (n = 1-10) chains, 2-D [CuCN](n) (n = 2-10) nanorings, and 3-D [Cu(n)(CN)(n)](m) (n = 4, m = 2, 3; n = 10, m = 2) tubes are investigated by means of a multitude of computational methodologies using density functional theory (DFT) and time-dependent-density-functional theory (TD-DFT) methods. The calculations revealed that the 2-D [CuCN](n) (n = 2-10) nanorings are more stable than the respective 1-D [CuCN](n) (n = 2-10) linear chains. The 2-D [CuCN](n) (n = 2-10) nanorings are predicted to form 3-D [Cun (CN)(n)](m) (n = 4, m = 2, 3; n = 10, m = 2) tubes supported by weak stacking interactions, which are clearly visualized as broad regions in real space by the 3D plots of the reduced density gradient. The bonding mechanism in the 1-D [CuCN](n) (n = 1-10) chains, 2-D [CuCN](n) (n = 2-10) nanorings, and 3-D [Cu(n)(CN)(n)](m) (n = 4, m = 2, 3; n = 10, m = 2) tubes are easily recognized by a multitude of electronic structure calculation approaches. Particular emphasis was given on the photophysical properties (absorption and emission spectra) of the [CuCN](n) chains, nanorings, and tubes which were simulated by TD-DFT calculations. The absorption and emission bands in the simulated TD-DFT absorption and emission spectra have thoroughly been analyzed and assignments of the contributing principal electronic transitions associated to individual excitations have been made.

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“…structural motifs in accommodating various ligand-imposed geometric requirements. [83][84][85][86] Specifically, sterically demanding chelates can function as capping ligands, effectively restricting spatial expansion of the structure to one dimension. 87 In the absence of chelating ligands, the parent Cu(I)/triazolate/CN À material [Cu 6 (trz)(CN) 5 ] ( 16) is isolated.…”

Section: Two-dimensional Structuresmentioning

confidence: 99%

Solid state coordination chemistry of metal-1,2,4-triazolates and the related metal-4-pyridyltetrazolates

2011

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Solid state coordination chemistry of the copper cyanide–organoamine system: hydrothermal synthesis and structural characterization of [{Cu2(bpy)2(CN)}2Cu5(CN)7]·0.17H2O

Cited by 55 publications

References 9 publications

Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

Electronic, bonding, and optical properties of 1d [CuCN]_n (n = 1–10) chains, 2d [CuCN]_n (n = 2–10) nanorings, and 3d [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods

Solid state coordination chemistry of metal-1,2,4-triazolates and the related metal-4-pyridyltetrazolates

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Solid state coordination chemistry of the copper cyanide–organoamine system: hydrothermal synthesis and structural characterization of [{Cu2(bpy)2(CN)}2Cu5(CN)7]·0.17H2O

Cited by 55 publications

References 9 publications

Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks

Electronic, bonding, and optical properties of 1d [CuCN]n (n = 1–10) chains, 2d [CuCN]n (n = 2–10) nanorings, and 3d [Cun(CN)n]m (n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods

Solid state coordination chemistry of metal-1,2,4-triazolates and the related metal-4-pyridyltetrazolates

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Electronic, bonding, and optical properties of 1d [CuCN]_n (n = 1–10) chains, 2d [CuCN]_n (n = 2–10) nanorings, and 3d [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods