10.1021/cg300415e.s001
Ana B. Caballero
Ana B.
Caballero
Antonio Rodríguez-Diéguez
Antonio
Rodríguez-Diéguez
Luis Lezama
Luis
Lezama
Juan M. Salas
Juan M.
Salas
Toward a New Type of Multifunctional
Metal–Organic
Systems Based on Nucleobase Analogues: First Results Derived From
The Use of Aliphatic α,ω-Dicarboxylates
American Chemical Society
2012
ligand
triazolopyrimidine derivatives
dimer
compound 5 exhibits
coordination modes
Mn
photoluminescent emission
Zn
73 nm
succinate
cm
malonate
New Type
dinuclear units
Stokes shift
Nucleobase Analogues
Cu
transition metal complexes
First Results Derived
2012-07-03 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Toward_a_New_Type_of_Multifunctional_Metal_Organic_Systems_Based_on_Nucleobase_Analogues_First_Results_Derived_From_The_Use_of_Aliphatic_Dicarboxylates/2508874
Five new transition metal complexes, containing the purine-mimetic
ligands 7-amine-1,2,4-triazolo[1,5-<i>a</i>]pyrimidine (7atp)
and 4,5-dihydro-5-oxo-1,2,4-triazolo[1,5-<i>a</i>]pyrimidine
(5HtpO), and also malonate (mal<sup>2–</sup>) and succinate
(suc<sup>2–</sup>) as secondary ligands are reported. Their
formula are [Mn<sub>2</sub>(μ-7atp)<sub>2</sub>(μ-mal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>1</b>), [Zn<sub>2</sub>(μ-7atp)<sub>2</sub>(μ-mal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), [Cu<sub>2</sub>(5HtpO)<sub>2</sub>(mal)<sub>2</sub>(H<sub>2</sub>mal)<sub>2</sub>(μ-H<sub>2</sub>O)<sub>2</sub>] (<b>3</b>), [Cu<sub>2</sub>(μ-5tpO)<sub>2</sub>(μ-Hsuc)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>4</b>), and [Cd<sub>2</sub>(μ-5tpO)<sub>2</sub>(μ<sub>4</sub>-suc)(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub> (<b>5</b>). Single-crystal X-ray analysis show that compounds <b>1</b>–<b>4</b> feature all dinuclear units with different
topologies while compound <b>5</b> exhibits a 3D-network with
small-diameter pores. The variety of coordination modes displayed
by both triazolopyrimidine derivatives together with the bridging
capability of the aliphatic α,ω-dicarboxylates used lead
to compounds with interesting structural features and physical properties.
The Cu(II) malonate dimer <b>3</b> exhibits weak ferromagnetic
interactions (<i>J</i> = +1.5 cm<sup>–1</sup>) while
a weak and a moderately strong antiferromagnetism are displayed, respectively,
in the Mn(II) (<i>J</i> = −2.1 cm<sup>–1</sup>) and Cu(II) succinate dimer <b>4</b> (<i>J</i> =
−109.7 cm<sup>–1</sup>). On the other hand, solid-state
photoluminescent emission is observed for the Zn(II) compound with
a Stokes shift of 73 nm.