4 years ago

Multistimuli Response Micro- and Nanolayers of a Coordination Polymer Based on Cu2I2 Chains Linked by 2-Aminopyrazine

Multistimuli Response Micro- and Nanolayers of a Coordination Polymer Based on Cu2I2 Chains Linked by 2-Aminopyrazine
J. Conesa-Egea, J. Gonzalez-Platas, F. Zamora, U. R. Rodríguez-Mendoza, J. I. Martínez, P. Ocón, V. Fernández-Moreira, P. Amo-Ochoa, J. Gallardo-Martínez, S. Delgado
A nonporous laminar coordination polymer of formula [Cu2I2(2-aminopyrazine)]n is prepared by direct reaction between CuI and 2-aminopyrazine, two industrially available building blocks. The fine tuning of the reaction conditions allows obtaining [Cu2I2(2-aminopyrazine)]n in micrometric and nanometric sizes with same structure and composition. Interestingly, both materials show similar reversible thermo- and pressure-luminescent response as well as reversible electrical response to volatile organic solvents such as acetic acid. X-ray diffraction studies under different conditions, temperatures and pressures, in combination with theoretical calculations allow rationalizing the physical properties of this compound and its changes under physical stimuli. Thus, the emission dramatically increases when lowering the temperature, while an enhancement of the pressure produces a decrease in the emission intensity. These observations emerge as a direct consequence of the high structural flexibility of the Cu2I2 chains which undergo a contraction in CuCu distances as far as temperature decreases or pressure increases. However, the strong structural changes observed under high pressure lead to an unexpected effect that produces a less effective CuCu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu2I2 chains for new applications. Lamellar semiconducting multistimuli coordination polymer based on Cu(I)-I-2-aminopyrazine chains is isolated in micro- and nanometric dimensions. The materials present high emission when temperature decreases and loses this emission with pressure, as a consequence of a shortening in CuCu distances. This apparent dilemma is rationalized by the use of theoretical calculations that demonstrate an ineffective overlapping of copper dz2 orbitals as pressure increases.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/smll.201700965

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