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

This is the peer reviewed version of the following article: Conesa‐Egea, J., Gallardo‐Martínez, J., Delgado, S., Martínez, J. I., Gonzalez‐Platas, J., Fernández‐Moreira, V., ... & Amo‐Ochoa, P. Multistimuli Response Micro‐and Nanolayers of a Coordination Polymer Based on Cu2I2 Chains Linked by 2‐Aminopyrazine. Small 13.33 (2017): 1700965 , which has been published in final form at https://doi.org/10.1002/smll.201700965. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionA 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 Cu-Cu 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 Cu-Cu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu2I2 chains for new applicationsThe authors thank financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P, MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2010-20843-C02-01, MAT2016-75586-C4-4-P, CTQ2016-75816-C2-1P), also thank the scientific computing center (CCC) of the Autonoma University of Madrid for their time. J.I.M. acknowledges the financial support by the Ramón y Cajal Program of MINECO (Grant RYC-2015-17730) and the EU via the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS