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Royal Society of Chemistry, CrystEngComm, 22(18), p. 4196-4204, 2016

DOI: 10.1039/c5ce02520f

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Two-step synthesis of heterometallic coordination polymers using a polyazamacrocyclic linker

This paper is available in a repository.
This paper is available in a repository.

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Abstract

A new macrocyclic linker 1,4,7,10-tetraazacyclododecane-1,7-bis(4-acetamidobenzoic)-4,10-diacetic acid (HL1) was synthesized and characterized. This linker was used to create two heterometallic coordination polymers following a two-step synthesis. This synthesis consisted of first combining this polyazamacrocyclic linker with Ni(ii) or Mn(ii) ions to obtain the corresponding metallomacrocyclic complexes showing non-coordinated carboxylic groups. In a second step, these metallated macrocycles were used as building units to construct two heterometallic Ni(ii)-Zn(ii) and Mn(ii)-Zn(ii) coordination polymers when combined with Zn(ii) ions. In addition, a third Zn(ii)-Zn(ii) coordination polymer could also be synthesized by direct mixing of HL1 with Zn(ii) ions. Interestingly, the Mn(ii)-Zn(ii) coordination polymer exhibits a reversible type-I >crystal-to-amorphous transformation> upon water sorption/desorption. ; This work was supported by MINECO-Spain through project PN MAT2012-30994. I. I. and J. A. thank MINECO for an RyC contract (RYC-2010-06530) and an FPU predoctoral grant (AP-2010-5934), respectively. ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2013-0295. ; Peer Reviewed