Light-induced electron transfer in Tl[Ag(CN)2]: Photochemical reaction of luminescent metal–metal exciplexes in the solid state

Srisook, Nattapong; Rizzolo, J. J.; Shankle, G. E.; Patterson, Howard H.

doi:10.1016/s0020-1693(99)00609-x

Cited by 8 publications

(8 citation statements)

References 14 publications

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“…The results here, however, are more closely related to the “optical memory” phenomenon reported by Zink and co-workers for Cu + - and Cu + /Ag + -doped β-alumina in which the crystal “remembers” which part of it had been irradiated. − The changes in the luminescence spectra upon laser irradiation are related to reversible photophysical processes in both the systems described here and those described by Zink. This is in contrast to two related studies for Pb[Au(CN) 2 ] 2 and TlAg(CN) 2 in which irradiation led to reversible photochemical and redox changes. , Here we describe the effect of laser irradiation and temperature on the luminescence properties of three dicyanoargentate(I) doped and pure crystals and the results are analyzed to show the effect of varying the Ag content on the rate of the “write/read/erase” process.…”

Section: Introductionmentioning

confidence: 61%

“…Previous work by our group [5][6][7]11,[18][19][20][21][27][28][29]30 and others [12][13][14][15][31][32][33][34] has demonstrated the propensity of Ag(I) species to aggregate either as pure complexes or as doped impurities in a host lattice despite the inherent weakness of the groundstate Ag(I)-Ag(I) interactions. We have shown that the argentophilic bonding in Ag(CN) 2species is a cooperative process.…”

Section: Discussionmentioning

confidence: 99%

“…This is in contrast to two related studies for Pb[Au(CN) 2 ] 2 and TlAg(CN) 2 in which irradiation led to reversible photochemical and redox changes. 27,28 Here we describe the effect of laser irradiation and temperature on the luminescence properties of three dicyanoargentate(I) doped and pure crystals and the results are analyzed to show the effect of varying the Ag content on the rate of the "write/ read/erase" process.…”

Section: Introductionmentioning

confidence: 99%

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“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

2003

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Laser irradiation of single crystals of doped Ag(CN)2 -/KCl and pure KAg(CN)2 at 77 K results in dramatic changes in their emission spectra. Higher-energy bands that were either absent or weak start appearing concomitant with a quenching of the original major lower-energy bands as samples are exposed to 266 nm laser light. These changes are progressive with increased irradiation time and they are also reversible. Thus, when a given crystal is heated from 77 K to ambient temperature and then re-cooled to 77 K, hysteresis occurs as the original luminescence spectra before irradiation are obtained. Two doped Ag(CN)2 -/KCl single crystals with Ag content of 1.21 and 2.23% (wt) as well as pure single crystals of KAg(CN)2 show this “write/read/erase” effect to various extents. By analyzing the luminescence profile versus exposure time to 266 nm laser irradiation at cryogenic temperatures, it was possible to calculate the rate constants for the forward (k 1) and reverse (k 2) reactions of the writing process. The fastest changes are for the 1.21% doped crystals (k 1 = 0.04493 min-1), followed by the 2.23% doped crystals (k 1 = 0.01245 min-1) while the slowest changes were for pure KAg(CN)2 (k 1 = 0.00178 min-1). The results were explained in terms of a change in the distribution of *[Ag(CN)2 -] n excitons with different geometries following laser irradiation.

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Section: Introductionmentioning

confidence: 61%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

2003

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“…807,808 It was subsequently observed that upon UV irradiation at low temperature, the emission intensity of Tl[Ag(CN) 2 ] would decrease and a nonemitting species would be produced. 809 The process was reversible upon heating the sample to ambient temperature to regenerate the original emitting species. A light-induced electron transfer mechanism was proposed for the photochemical reaction.…”

Section: Light-emitting Silver(i) Self-assembled Materialsmentioning

confidence: 99%

Light-Emitting Self-Assembled Materials Based on d⁸ and d¹⁰ Transition Metal Complexes

2015

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“…As previously mentioned, our group reported extensively on the optical memory of d 10 cyanometallates [16,17,23,30,82]. In many of these cases the optical memory behavior is the result of a photo-induced electron transfer [18,24,82]. For example, in the instance of Tl[Ag(CN) 2 ] irradiation at 78 K using a 318 nm laser results in the formation of a redox active [Ag(CN) 2 ] 3 3− trimer.…”

Section: Resultsmentioning

confidence: 99%

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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Light-induced electron transfer in Tl[Ag(CN)2]: Photochemical reaction of luminescent metal–metal exciplexes in the solid state

Cited by 8 publications

References 14 publications

“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

Light-Emitting Self-Assembled Materials Based on d⁸ and d¹⁰ Transition Metal Complexes

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

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Light-induced electron transfer in Tl[Ag(CN)2]: Photochemical reaction of luminescent metal–metal exciplexes in the solid state

Cited by 8 publications

References 14 publications

“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

“Write/Read/Erase” with Laser Irradiation of Dicyanoargentate(I) Doped and Pure Crystals

Light-Emitting Self-Assembled Materials Based on d8 and d10 Transition Metal Complexes

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

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Light-Emitting Self-Assembled Materials Based on d⁸ and d¹⁰ Transition Metal Complexes