Next Article in Journal
Thermo–Mechanical Behavior and Constitutive Modeling of In Situ TiB2/7050 Al Metal Matrix Composites Over Wide Temperature and Strain Rate Ranges
Previous Article in Journal
Study of Toughness and Macro/Micro-Crack Development of Fibre-Reinforced Ultra-High Performance Concrete After Exposure to Elevated Temperature
Open AccessArticle

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

1
Department of Chemistry, University of Maine, Orono, ME 04469, USA
2
Department of Chemistry, College of William and Mary, Williamsburg, VA 23187-8795, USA
*
Author to whom correspondence should be addressed.
Materials 2019, 12(8), 1211; https://doi.org/10.3390/ma12081211
Received: 24 March 2019 / Revised: 7 April 2019 / Accepted: 10 April 2019 / Published: 12 April 2019
(This article belongs to the Special Issue Advances and Evolutions in Optical Data Storage)
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 CuCu 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. View Full-Text
Keywords: luminescence; crystallography; optical memory; charge transfer; copper cyanide luminescence; crystallography; optical memory; charge transfer; copper cyanide
Show Figures

Graphical abstract

MDPI and ACS Style

Nicholas, A.D.; Bullard, R.M.; Wheaton, A.M.; Streep, M.; Nicholas, V.A.; Pike, R.D.; Patterson, H.H. Synthesis and Luminescence of Optical Memory Active Tetramethylammonium Cyanocuprate(I) 3D Networks. Materials 2019, 12, 1211.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Search more from Scilit
 
Search
Back to TopTop